USO10968362B2

( 12) United States Patent ( 10 ) Patent No .: US 10,968,362 B2

Carella et al . (45 ) Date of Patent : Apr. 6, 2021
( 54 ) FLUORINATED SURFACTANT - FREE ( 58 ) Field of Classification Search
AQUEOUS DISPERSION OF A VINYLIDENE CPC CO9D 127/16 ; CO9D 5/24 ; HO1M 2/166 ;
FLUORIDE COPOLYMER COMPRISING HO1M 2/145 ; HO1M 2/1686 ; CO8F
HYDROXYL GROUPS 215/225
See application file for complete search history .
( 71 ) Applicant: SOLVAY SPECIALTY POLYMERS
ITALY S.P.A., Bollate (IT ) ( 56 ) References Cited
( 72 ) Inventors: Serena Carella , Parabiago ( IT ) ; Elena U.S. PATENT DOCUMENTS
Molena , Bollate ( IT ) ; Maurizio Biso ,
Milan ( IT ) ; Giulio Brinati , Milan (IT) 5,880,204 A 3/1999 McCarthy et al.
2010/0133482 A1 * 6/2010 Abusleme B01D 71/76
( 73 ) Assignee : SOLVAY SPECIALTY POLYMERS 252/511
ITALY S.P.A., Bollate (IT )
FOREIGN PATENT DOCUMENTS
( * ) Notice: Subject to any disclaimer, the term of this
patent is extended or adjusted under 35 EP 791973 A2 8/1997
U.S.C. 154 ( b ) by 96 days. WO 2008129041 A1 10/2008
WO 2013010936 A1 1/2013
WO 2013120858 Al 8/2013
( 21 ) Appl . No .: 16 /318,128 WO 2014095907 A1 6/2014
WO 2015059155 Al 4/2015
(22 ) PCT Filed : Jul . 12 , 2017 WO 2016003748 A1 1/2016
( 86) PCT No .: PCT /EP2017 /067482 OTHER PUBLICATIONS
$ 371 (c ) ( 1 ) , Pianca, M. et al . , “ End groups in fluoropolymers ”, Journal of
( 2 ) Date : Jan. 15 , 2019
Fluorine Chemistry, 1999 , vol . 95 , pp . 71-84 — Elsevier Science SA .
( 87 ) PCT Pub . No .: WO2018 /011244 Standard ASTM D3835-08 , " Standard Test Method for Determina
tion of Properties of Polymeric Materials by Means of a Capillary
PCT Pub . Date : Jan. 18 , 2018 Rheometer ” , ASTM International, 2008 , 11 pages .
( 65 ) Prior Publication Data * cited by examiner
US 2019/0284428 A1 Sep. 19 , 2019 Primary Examiner Robert D Harlan
( 30 ) Foreign Application Priority Data (74 ) Attorney, Agent, or Firm — Osha Bergman Watanabe
& Burton LLP
Jul . 15 , 2016 ( EP ) 16179636
( 57 ) ABSTRACT
( 51 ) Int. Cl.
HOIM 2/14 ( 2006.01 ) The present invention pertains to a fluorosurfactant free
HOIM 2/16 ( 2006.01 ) aqueous dispersion of an acrylic -modified vinylidene fluo
C08F 214/22 ( 2006.01 ) ride polymer, possessing a melt viscosity of at least 30
CO9D 5/24 ( 2006.01 ) kPoise , and possessing an amount of end groups of formula
C09D 127/16 ( 2006.01 ) CH , OH of at least 5 mmol/kg, to a method for its
( 52) U.S. CI. preparation and to its use for the manufacture of electro
CPC C09D 127/16 (2013.01 ) ; C08F 214/225 chemical cell components, such as electrodes and / or com
( 2013.01 ) ; C09D 5/24 ( 2013.01 ) ; HOIM 2/145 posite separators.
(2013.01 ) ; HOTM 2/166 (2013.01 ) ; HOIM
2/1686 (2013.01 ) 20 Claims , No Drawings
 US 10,968,362 B2
1 2
FLUORINATED SURFACTANT- FREE tional level in an organic solvent. An electrode- forming
AQUEOUS DISPERSION OF A VINYLIDENE composition is formed by dispersing powdery electrode
FLUORIDE COPOLYMER COMPRISING material in the binder solution and is applied onto an
HYDROXYL GROUPS electroconductive substrate, followed by drying, to form a
5 composite electrode layer, which retains the powdery elec
CROSS - REFERENCE TO RELATED trode material at a smaller amount of vinylidene fluoride
APPLICATION polymer than a conventional level and is well resistant to a
non- aqueous electrolytic solution .
This application is a U.S. national stage entry under 35 In this field , hence, a continuous quest exists for aqueous
U.S.C. $ 371 of International Application No. PCT/EP2017/ 10 dispersions of VDF polymers possessing all required prop
067482 filed Jul . 12 , 2017 , which claims priority to Euro- erties for being used in the field of components for second
pean application No. EP 16179636.2 filed on Jul . 15 , 2016 . ary batteries, including notably ability to deliver cohesion
The entire contents of these applications are explicitly with electrode active materials and /or with composite sepa
incorporated herein by this reference . rators ' inorganic fillers , ability to ensure adhesion to metal
15 collectors , separator porous substrates, stability /non -disso
TECHNICAL FIELD lution towards liquid electrolyte solutions and prevention of
contamination with chemicals possibly interfering with elec
The present invention pertains to a vinylidene fluoride trochemical reactions (e.g. fluorosurfactant having not suf
polymer aqueous dispersion, to a method for its preparation ficient electrochemical stability ) , while yet possessing
and to its use for the manufacture of electrochemical cell 20 adequate properties for processing, including shear stability
components, such as electrodes and / or composite separators. during formulation and casting , acceptable shelf life.
Now, techniques for manufacturing VDF dispersions are
BACKGROUND ART generally based on aqueous emulsion polymerization , gen
erally in the presence of fluorinated emulsifiers, which are
Vinylidene fluoride (VDF ) polymers are known in the art 25 generally difficult to be removed from resulting dispersions,
to be suitable as binders for the manufacture of electrodes and which may have detrimental effects as contaminants in
and / or composite separators, and /or as coatings of porous electrochemical devices parts. While attempts to reduce or
separators for use in non -aqueous - type electrochemical even eliminate fluorosurfactants in emulsion polymerization
devices such as batteries, preferably secondary batteries, and of VDF so as to deliver stable VDF polymers dispersions
electric double layer capacitors. 30 free therefrom are known, those techniques are understood
Leading materials which are available in the marketplace to be based to self - stabilization of polymer chains through
for this field of use are VDF polymers powders which may end groups ' chemistry . Increasing molecular weight would
be modified by incorporation of polar groups , and which are reduce hence overall concentration of chain ends , leading
processed by dissolution in solvent systems which generally hence to lack of stabilization phenomena.
comprises N -methyl pyrrolidone or mixtures of N -methyl 35 U.S. Pat . No. 5,880,204 ( ALLIED SIGNAL INC ) 9 Mar.
pyrrolidone and a diluting solvent such as acetone , propyl 1999 discloses room temperature coalesceable aqueous fluo
acetate , methyl ethyl ketone and ethyl acetate . Exemplary ropolymer dispersions comprising particles of a block copo
materials are e.g. disclosed in EP 2147029 A (SOLVAY lymer having a first semi-crystalline block and a second
SOLEXIS SPA ) 27 Jan. 2010 provide for linear semi- amorphous block , wherein first and second block are gen
crystalline copolymers comprising recurring units derived 40 erally VDF or CTFE copolymers , and second block com
from vinylidene fluoride (VDF ) monomer and at least one prises generally a so - called “ cure - site provider ” , which can
hydrophilic (meth ) acrylic monomer, having improved ther- be notably an acid such as acrylic acid . Generally the
mal stability and delivering outstanding cohesion when used fluoropolymer, as a whole , possesses Mw of 10,000 to
as binder in batteries. 1,000,000 ( hence ranging from low to extremely high
While technologies based on the dissolution in an organic 45 molecular weight). These dispersions are taught useful as
solvent of VDF polymers have been pursued, the interest in floor polishes . Generally, latices are prepared in the absence
water - borne dispersions is increasing, driven by both eco- of surfactants, using a redox initiating system at relatively
nomic and environmental aspects . To effectively employ low polymerization temperature.
waterborne polymer compositions in electrode- or separator- WO 2013/010936 (SOLVAY SPECIALTY POLYMERS
forming processes, it is important to develop systems nota- 50 ITALY SPA ) 24 Jan. 2013 pertains to an aqueous composi
bly having sufficient stability prior and after admixing with tion comprising: ( A ) an aqueous latex comprising at least
e.g. powdery electrode material or fillers, suitable filmability one vinylidene fluoride (VDF ) polymer (polymer (F ) ] com
and processing characteristics for being advantageously prising recurring units derived from vinylidene fluoride
applied onto required support ( e.g. metal collector) via (VDF ) and at least one (meth ) acrylic monomer (MA ) which
standard techniques and for yielding a uniform layer. Most 55 is preferably AA , ( B ) at least one powdery electrode mate
importantly, these binder systems should provide proper rial, and ( C ) optionally, less than 10 percent by weight,
cohesion within the hosted particles and proper adhesion of based on the total weight of the aqueous composition , of at
the same to the support after drying. least one organic solvent ( S ) , wherein the polymer (F ) in the
Further, in the area of VDF polymers powders , it has been aqueous latex is under the form of primary particles having
generally recognized that a high molecular weight is ben- 60 an average primary particle size of less than 1 um , as
eficial for this field of use . Notably, EP 0791973 A measured according to ISO 13321. This document also
(KUREHA ) 27 Aug. 1997 pertains to a binder solution for pertains to a process for manufacturing an electrode using
providing an electrode suitable for use in non -aqueous - type said aqueous composition, to an electrode comprising a
electrochemical devices, such as a battery and an electric metal substrate coated on at least one surface with said
double layer capacitor, which is formed by dissolving a 65 aqueous composition and to use of said electrode for manu
vinylidene fluoride polymer having an inherent viscosity facturing a non - aqueous- type electrochemical device . The
( and thus a polymerization degree) higher than a conven- latices are prepared by aqueous emulsion polymerization at
 US 10,968,362 B2
3 4
pressure of 20 to 70 bar and temperatures of 60 to 135º C. , units derived from vinylidene fluoride (VDF ) monomer and
preferably 90 to 130 ° C. , in the presence of a micro- recurring units derived from at least one hydrophilic (meth )
emulsion or of a fluorosurfactant. acrylic monomer (MA ) of formula:
WO 2015/059155 ( SOLVAY SA) 30 Apr. 2015 is directed
to an electrode - forming composition comprising: ( a ) an 5 R2 R3
aqueous latex comprising at least one fluoropolymer (poly
mer (F ) ] comprising recurring units derived from vinylidene
fluoride (VDF ) , at least one hydrogenated monomer, which R1 R
is preferably AA , and, optionally, at least one other fluori 10 OH
nated monomer different from VDF, and , homogeneously
dispersed therein , (b ) at least one powdery electrode -form
ing material consisting of Sulphur, ( c ) at least one powdery wherein each of R1 , R2 , R3 , equal or different from each
electrically conducting material, wherein the polymer ( F ) in other, is independently an hydrogen atom or a C -Cz hydro
a hydroxyl group or a C1 - C5
theaqueouslatexisundertheformof primaryparticles 15 hydrocarbon moietycomprisingatleast onehydroxyl group,
having an average primary particle size of less than 1 um , as said polymer ( A )
measured according to ISO 13321. This document also
pertains to a process for the manufacture of said composition ( i ) comprising more than 85.0 % moles of recurring units
and to use of said composition in a process for the manu derived from VDF and from 0.05 to 10 % by moles of
recurring units derived from said hydrophilic (meth )acrylic
facture of a positive electrode for a Lithium -Sulphur battery. 20 monomer
The latices are prepared by aqueous emulsion polymeriza ring units (ofMApolymer ) , with respect to the total number of recur
( A );
tion at pressure of 20 to 70 bar and temperatures of 60 to
135º C. , preferably 90 to 130 ° C. , po oly in the presence determined at a shear rateviscosity
( ii ) possessing a melt of at least 30 kPoise , when
of 100 sec - 1 , and at a temperature
of a micro - emulsion or a fluorosurfactant.
WO 2008/129041 (SOLVAY SOLEXIS SPA ) 30 Oct. 25 of (230 ° C., according to ASTM D3835 , and
iii ) possessing an amount of end groups of formula
2008 is directed to a linear semi-crystalline copolymer
comprising recurring units derived from vinylidene fluoride CH2 - OH of at least 5 mmol /kg and at most 20 mmol/kg;
(VDF ) monomer and at least one hydrophilic (meth )acrylic wherein said dispersion ( D ) is substantially free from
monomer which is statistically distributed in the polymer 30 fluorinated surfactants .
chain , and to a method for its manufacture by suspension The invention further pertains to a method of making the
polymerization combined with step - wise addition of acrylic said dispersion ( D ) , said method comprising emulsion
monomer . polymerization of VDF and said hydrophilic (meth )acrylic
WO 2013/120858 ( SOLVAY SPECIALTY POLYMERS monomer (MA ) in the presence of a persulfate inorganic
ITALY SPA ) 22 Aug. 2013 is directed to a process for the 35 initiator, at a temperature of at most 80 ° C. , under a pressure
manufacture of a composite separator for an electrochemical of at least 20 bar, without adding any fluorinated surfactant.
cell , said process comprising the following steps : (i ) pro- The Applicant has surprisingly found that this manufac
viding a substrate layer; ( ii ) providing a coating composition turing method enables producing a dispersion possessing
comprising : sufficient stability against coagulation, so as to ensure
an aqueous latex comprising at least one VDF polymer 40 adequate shelf -life and processability in the absence of
fluorinated surfactants, while achieving high molecular
latex, and weight of resulting modified VDF polymer, so as to provide
at least one non - electroactive inorganic filler material; for outstanding behaviour in electrochemical cell compo
(iii ) applying said coating composition onto at least one nents ' field of use .
surface of said substrate layer to provide a coating compo
sition layer ; and 45
(iv ) drying said coating composition layer. DESCRIPTION OF EMBODIMENTS
WO 2014/095907 (SOLVAY SPECIALTY POLYMERS
ITALY SPA ) 26 Jun . 2014 pertains to a process for the Polymer ( A ) comprises recurring units derived from
derived from vinylidene fluoride (VDF ) and from at least
manufacture of a dense film , said process comprising pro 50 one
viding a solid composition of a VDF fluoropolymer com hydrophilic (meth )acrylic monomer (MA ).
prising carboxylic groups and at least one PAO ; and pro- The polymer (A) may further comprise recurring units
cessing said mixture in molten phase thereby providing a derived from at least one other comonomer ( C ) different
dense film , which can be used as dense separator in elec from VDF and from monomer (MA ), as above detailed .
trochemical devices . 55
The comonomer ( C) can be either a hydrogenated
There is a continuous shortfall in the art for aqueous comonomer [ comonomer (H ) ] or a fluorinated comonomer
dispersions of polar modified VDF polymers which possess [ comonomer (F ) ] .
improved performances in Li batteries' application , but By the term “ hydrogenated comonomer
which yet possess substantial latex stability to deliver appro- [ comonomer ( H ) ]”, it is hereby intended to denote an
priate shelf life and processability. 60 ethylenically unsaturated comonomer free of fluorine atoms .
Non - limitative examples of suitable hydrogenated
SUMMARY OF INVENTION comonomers ( H ) include, notably , ethylene, propylene,
vinyl monomers such as vinyl acetate, as well as styrene
The Applicant has now found that a solution to the above monomers , like styrene and p -methylstyrene.
defined problem is provided by an aqueous dispersion 65 By the term “ fluorinated comonomer [ comonomer ( F ) ]” ,
[ dispersion ( D )] comprising particles of a vinylidene fluo- it is hereby intended to denote an ethylenically unsaturated
ride (VDF ) copolymer ( polymer (A) ] comprising recurring comonomer comprising at least one fluorine atom .
 US 10,968,362 B2
5 6
The comonomer ( C ) is preferably a fluorinated comono- hydrophilic (meth )acrylic monomer (MA ) as above
mer ( comonomer ( F ) ] . described. In the rest of the text , the expressions “ hydro
Non - limitative examples of suitable fluorinated comono- philic (meth )acrylic monomer ( MA ) ” and “ monomer (MA )"
mers ( F ) include , notably, the followings: are understood, for the purposes of the present invention ,
( a ) C2 -Cg fluoro- and/or perfluoroolefins such as tetrafluo- 5 both in the plural and the singular, that is to say that they
denote both one or more than one hydrophilic (methacrylic
roethylene ( TFE ) , hexafluoropropylene ( HFP ) , pentafluoro
propylene and hexafluoroisobutylene; monomer (MA) .
( b ) C2 - Cg hydrogenated monofluoroolefins such as vinyl According to certain embodiments, polymer ( A ) consists
fluoride, 1,2 - difluoroethylene and trifluoroethylene; essentially of recurring units derived from VDF , and from
(c) perfluoroalkylethylenes of formula CH2= CH RO 10 monomer (MA ).
According to other embodiments, polymer ( A ) consists
wherein Ro is a C.-C. perfluoroalkyl group ;
(d) chloro- and / or bromo- and / or iodo - C2 -C6 fluoroolefins essentially
and from
of recurring units derived from VDF, from HFP
monomer (MA ).
such as chlorotrifluoroethylene ( CTFE ) ; Polymer ( A ) may still comprise other moieties such as
( e ) ( per)fluoroalkylvinylethers of formula CFz = CFOR
wherein R , is a C- C, fluoro- or perfluoroalkyl group, e.g. 15 defects
impair ,itsendphysico
-groups- chemical
and the properties
like, which. do not affect nor
CF3, C2F5 , C3F7 ; The hydrophilic (meth acrylic monomer ( MA ) preferably
( f) ( per ) fluoro -oxyalkylvinylethers of formula complies formula :
CF2 = CFOX , wherein X , is a C , -C12 oxyalkyl group or a
C1 - C12 (per ) fluorooxyalkyl group having one or more ether 20
groups , e.g. perfluoro - 2 -propoxy -propyl group ; R2 R3
fluoroalkyl -methoxy - vinylethers of formula
CF = CFOCF , OR ,2, wherein R , is a C -C fluoro- or per
fluoroalkyl group , e.g. - CF3, C2F5 , CzF , or a C1 - C6 R1 R
OH
( per ) fluorooxyalkyl group having one or more ether groups , 25
e.g. -CF 0 CF ;
( h ) fluorodioxoles of formula :
wherein each of R1 , R2 , RoH have the meanings as above
defined , and R3 is hydrogen ; more preferably, each of R1 ,
R13 RA R2 , R3 are hydrogen , while Roh has the same meaning as
30 above detailed .
Non limitative examples of hydrophilic (methacrylic
monomers (MA ) are notably acrylic acid , methacrylic acid ,
hydroxyethyl (meth ) acrylate, hydroxypropyl(meth )acrylate ;
Ros Rf6 hydroxyethylhexylmethacrylates .
35 The monomer (MA ) is more preferably selected among :
hydroxyethylacrylate (HEA ) of formula:
wherein each of R3, R14, Rys and R76, equal to or different
from each other, is independently a fluorine atom , a C2 - C6
fluoro- or perhalo ) fluoroalkyl group , optionally comprising H
one or more oxygen atoms, e.g. - CF3, C2F5 , C3F7 , 40 H
OCF3, OCF CF2OCF3.
Most preferred fluorinated comonomers (F ) are tetrafluo
roethylene (TFE ) , trifluoroethylene ( TrFE ), chlorotrifluoro H
ethylene ( CTFE ) , hexafluoropropylene ( HFP ) , perfluorom OH
ethyl vinyl ether ( PMVE) , perfluoropropyl vinyl ether 45
( PPVE ) and vinyl fluoride, and among these, HFP is most 2 - hydroxypropyl acrylate (HPA ) of either of formulae:

ya ye
preferred.
Should at least one comonomer (C ) ( preferably HFP ) be
present, the polymer ( A ) comprises typically from 0.05 % to
14.5 % by moles , preferably from 1.0 % to 13.0 % by moles , 50 H
of recurring units derived from said comonomer ( s ) ( C) , with
respect to the total moles of recurring units of polymer ( A ).
However, it is necessary that the amount of recurring units CH3 OH
derived from vinylidene fluoride in the polymer (A) is at
least 85.0 mol % , preferably at least 86.0 mol % , more 55 CH3
preferably at least 87.0 mol % , so as not to impair the
excellent properties of vinylidene fluoride resin , such as
chemical resistance, weatherability, and heat resistance . For acrylic acid (AA ) of formula :
instance, when polymer ( A ) comprises an amount of VDF
units of less than 85.0 mol % , it cannot be used for 60 H
formulating coating compositions for making composite
separators for batteries, as the corresponding polymer would
dissolve in the liquid solvent used as electrolyte liquid
phase.
The term “ at least one hydrophilic (methacrylic mono-
mer (MA ) " is understood to mean that the polymer ( A ) may
comprise recurring units derived from one or more than one
65
H

and mixtures thereof.

Y
H OH
 US 10,968,362 B2
7 8
More preferably, the monomer (MA ) is AA and / or HEA , Excellent results have been obtained when the polymer
even more preferably is AA . ( A ) comprised an amount of polar end groups of formula
Determination of the amount of (MA) monomer recurring CH2 OH of at least 5 mmol /kg, and at most 10 mmol/kg.
units in polymer ( A ) can be performed by any suitable Typically , polymer ( A ) comprises, in addition to polar end
method . Mention can be notably made of acid - base titration 5 groups of formula CH , OH , non -polar end groups,
methods, well suited e.g. for the determination of the acrylic including groups of any of formulae CF2H and
acid content, of NMR methods, adequate for the quantifi- CF CH .
cation of (MA ) monomers comprising aliphatic hydrogens The total amount of end groups of any of formulae
in side chains ( e.g. HPA , HEA) , of weight balance based on 10 CH2OH , CF2H and —CF2CH2 in the polymer ( A ) is
total fed (MA) monomer and unreacted residual (MA ) advantageously of not more than 70 mmol/kg, preferably of
monomer during polymer ( A ) manufacture . not more than 67 mmol/kg, even more preferably of not
Polymer (A) comprises preferably at least 0.1 , more more than 65 mmol/kg. Total amount of end groups of
preferably at least 0.2 % moles of recurring units derived formulae - CH2 - OH , CF2H and CF2CH2 in the above
from said hydrophilic (meth )acrylic monomer (MA ) and / or 15 indicated range is representative of polymers ( A ) having
polymer (A) comprises preferably at most 10 , more prefer- linear structure and high molecular weight, as required for
ably at most 7.5 % moles , even more preferably at most 5 % the hereby intended field of use .
moles , most preferably at most 3 % moles of recurring units As said, dispersion (D ) is substantially free from fluori
derived from said hydrophilic (meth )acrylic monomer nated surfactants .
(MA ). 20 The expression “ substantially free” in combination with
Generally, particles of polymer ( A ) possess a primary the amount of fluorinated surfactants in dispersion (D ) is to
particle average size of less than 1 um . For the purpose of be meant to exclude the presence of any significant amount
the present invention , the term “ primary particles ” is of said fluorinated surfactants, e.g. requiring the fluorinated
intended to denote primary particles of polymer ( A ) deriving surfactants to be present in an amount of less than 5 ppm ,
directly from aqueous emulsion polymerization, without 25 preferably
1 ppm , withofrespect
less thanto 3theppmtotal, more preferably
weight of less(Dthan) .
of dispersion
isolation of the polymer from the emulsion (i.e. the latex ) . The aqueous emulsion polymerization process as detailed
Primary particles of polymer (A) are thus to be intended above
distinguishable from agglomerates ( i.e. collection of pri radicalisinitiator
typically carried out in the presence of at least one
.
mary particles ), which might be obtained by recovery and
conditioning steps of such polymer manufacture such as 30 70 bar, preferably pressure
Polymerization ranges typically between 20 and
between 25 and 65 bar.
concentration and / or coagulation of aqueous latexes of the While the choice of the persulfate radical initiator is not
polymer (A) and subsequent drying and homogenization to particularly limited , it is understood that radical initiators
yield the respective powder.
The dispersion (D ) of the invention is thus distinguishable suitable for an aqueous emulsion polymerization process are
from an aqueous slurry that can be prepared by dispersing 35 selectedthefrompolymerization
compounds capable of initiating and / or accel
powders a polymer in an aqueous medium . The average erating process and include, but are not
particle size of powders of a polymer or copolymer dis limited to , sodium , potassium and ammonium persulfates.
One or more radical initiators as defined above may be
persed in an aqueous slurry is typically higher than 1 um , as added
measured according to ISO 13321 . to the aqueous medium as defined above in an amount
Preferably, the primary particles average size of the 40 ranging advantageously from 0.001 % to 20 % by weight
particles of polymer ( A ) in dispersion (D ) is above 20 nm , based on the weight of the aqueous medium .
As said , the method is carried out with no addition of a
more preferably above 30 nm , even more preferably above fluorinated surfactant (FS ) complying with formula (III )
50 nm , and / or is below to 600 nm , more preferably below
400 and even more preferably below 350 nm as measured here below :
according to ISO 13321 . 45
R $ (X )/ ( M * )k (III)
As above said , polymer ( A ) possesses a melt viscosity
(MV ) of at least 30 kPoise , when determined at a shear rate wherein :
of 100 sec- ?, and at a temperature of 230 ° C. , according to Rys is selected from a C3 -C16 ( per ) fluoroalkyl chain,
ASTM D3835 . The MV of polymer (A) is not particularly optionally comprising one or more catenary or non
limited , but it is generally understood that MV of no more 50 catenary oxygen atoms, and a (per ) fluoropolyoxyalkyl
than 100 kPoise , preferably less than 80 kPoise will be chain ,
adequate for ensuring optimal properties in electrochemi- X - is selected from COO , -PO , - and SO , ,
cals' applications. M * is selected from NH4+ and an alkaline metal ion , and
Furthermore, the polymer (A) is required to comprise an k is 1 or 2 .
amount of polar end groups of formula – CH2 - OH of at 55 Non - limitative examples of fluorinated surfactants (FS )
least 5 mmol/kg, when determined by ' H -NMR according to whose presence is substantially avoided in dispersion ( D )
PIANCA , Maurizio , et al . End Groups in fluoropolymers . are the followings:
Journal of Fluorine Chemistry. 1999 , vol . 95 , p . 71-84 . ( a ) CF (CF ), COOM ', wherein n , is an integer ranging
The Applicant has surprisingly found that a delicate from 4 to 10 , preferably from 5 to 7 , preferably n? being
equilibrium between high molecular weight and number of 60 equal to 6 , and M' represents NH4 , Na , Li or K , preferably
polar end groups has to be fulfilled , as required in the NH ;
dispersion ( D ) for ensuring appropriate colloidal stability. ( b ) T-(CzF.0 ) ( CFXO ) , CF COOM ", wherein T repre
In preferred embodiments, the polymer ( A ) comprises an sents a Cl atom or a perfluoroalkoxyde group of formula
amount of polar end groups of formula CH2 - OH of at C F2x +1- C140 , wherein x is an integer ranging from 1 to 3
least 5 mmol/kg, and / or advantageously at most 18 mmol/ 65 and x' is 0 or 1 , n , is an integer ranging from 1 to 6 , mi is
kg , preferably at most 15 mmol /kg, even more preferably at an integer ranging from 0 to 6 , M " represents NH4 , Na , Li
most 12 mmol/kg. or K and X represents F or CF3 ;
 US 10,968,362 B2
9 10
( c ) F– ( CF2CF2 )n2 - CH2 CH2 - ROZM ", in which R is a relatively large specific surface area compared with those
a phosphorus or a sulphur atom , preferably R being a of active substances for batteries.
sulphur atom , M " represents NH4 , Na , Li or K and nz is an The preferred electrode - forming composition for positive
integer ranging from 2 to 5 , preferably n , being equal to 3 ; electrodes comprises:
( d ) ARB- bifunctional fluorinated surfactants , 5 ( a) polymer ( A ), in an amount from 1 to 10 % wt ,
wherein A and B , equal to or different from each other, have preferably
with
from 2 to 9 % wt , more preferably about 3 % wt ,
respect to the total weight ( a) + (b ) + (c ) ;
formula (O ), CFX " _COOM *, wherein M * represents
NH4 , Na , Li or K , preferably M * representing NH4 , X " is F tive(b, )incarbon black as electroconductivity - imparting addi
an amount from 2 to 10 % wt , preferably from 4 to
or CFz and p is an integer equal to 0 or 1 , and Rof is a
divalent (per )fluoroalkyl or (per ) fluoropolyether chain such 10 total
6 % wt , more preferably about 5 % wt , with respect to the
weight ( a) + (b ) + ( c ) ;
that the number average molecular weight of A -Rbf B is in
the range of from 300 to 1800 ; and ( c ) a powdery electrode material, preferably a composite
( e ) mixtures thereof.
metal chalcogenide represented by a general formula of
LIMY2, as above detailed , in an amount from 80 to 97 % wt ,
An aqueous
obtained electrode
by adding and -dispersing
forming composition may be
a powdery electrode 15 wtpreferably
.
from 85 to 94% wt, more preferably about 92 %
material (an active substance for a battery or an electric An aqueous coating composition suitable for coating
double layer capacitor ), and optional additives , such as an separators can be obtained by adding and dispersing a
electroconductivity - imparting additive and / or a viscosity non - electroactive inorganic filler material, and optional
modifying agent, into the dispersion (D ) , as above detailed . 20 additives, into the dispersion (D ) , as above detailed .
Also an object of the invention is thus an aqueous Also an object of the invention is thus an aqueous coating
electrode - forming composition comprising dispersion ( D ) , composition [ composition (AC )] comprising dispersion (D ) ,
as above detailed , a powdery electrode material and , option- as above detailed, at least one non - electroactive inorganic
ally, an electroconductivity - imparting additive and /or a vis- filler material and , optionally, one or more than one addi
cosity modifying agent. 25 tional additive .
Among viscosity modifying agents, a thickener may be By the term “ non -electroactive inorganic filler material” ,
added in order to prevent or slow down the settling of the it is hereby intended to denote an electrically non -conduct
powdery electrode material from the aqueous composition ing inorganic filler material which is suitable for the manu
of the invention . Non - limitative examples of suitable thick- facture of an electrically insulating separator for electro
eners include , notably, organic thickeners such as partially 30 chemical cells .
neutralized poly (acrylic acid ) or poly (methacrylic acid ) , The non - electroactive inorganic filler material in the
carboxylated alkyl cellulose like carboxylated methyl cel- separator according to the invention typically has an elec
lulose and inorganic thickeners such as natural clays like trical resistivity (p ) of at least 0.1x10 ohm cm , preferably of
montmorillonite and bentonite, manmade clays like laponite at least 0.1x1012 ohm cm , as measured at 20 ° C. according
and others like silica and talc . 35 to ASTM D 257. Non- limitative examples of suitable non
In the case of forming a positive electrode for a lithium electroactive inorganic filler materials include , notably,
ion battery, the active substance may comprise a composite natural and synthetic silicas , zeolites , aluminas , titanias ,
metal chalcogenide represented by a general formula of metal carbonates, zirconias, silicon phosphates and silicates
LIMY2 , wherein M denotes at least one species of transition and the like . The non - electroactive inorganic filler material
metals such as Co , Ni , Fe , Mn, Cr and V ; and Y denotes a 40 is typically under the form of particles having an average
chalcogen, such as Oor S. Among these, it is preferred to use size of from 0.01 um to 50 um , as measured according to
a lithium -based composite metal oxide represented by a ISO 13321 .
general formula of LiMO2 , wherein M is the same as above. Optional additives in composition ( AC ) include notably
Preferred examples thereof may include: LiC002 , LiNiO2 , viscosity modifiers, as detailed above, anti- foams, non
LiNi , C01.0 , ( 0 < x < 1), and spinel - structured LiMn, 04 45 fluorinated surfactants, and the like .
In the case of forming a negative electrode for a lithium Among non - fluorinated surfactants, mention can be made
battery, the active substance may preferably comprise a of non - ionic emulsifiers, such as notably alkoxylated alco
carbonaceous material, such as graphite , activated carbon or hols , e.g. ethoxylates alcohols , propoxylated alcohols ,
a carbonaceous material obtained by carbonization of phe- mixed ethoxylated /propoxylated alcohols ; of anionic surfac
nolic resin , pitch, etc. The carbonaceous material may 50 tants, including notably fatty acid salts , alkyl sulfonate salts
preferably be used in the form of particles having an average (e.g. sodium dodecyl sulfate ), alkylaryl sulfonate salts , ary
diameter of ca. 0.5-100 um . lalkyl sulfonate salts , and the like .
An electroconductivity -imparting additive may be added The composition (AC ) may be obtained from the disper
in order to improve the conductivity of a resultant composite sion ( D ) , e.g. ( i ) by formulating dispersion ( D ) with optio
electrode layer formed by applying and drying of the elec- 55 additives, as above detailed , ( ii ) by upconcentrating disper
trode- forming composition of the present invention , particu- sion (D ) , notably through standard techniques like ultra
larly in case of using an active substance, such as LiC002 , filtration , clouding , and the like , (iii ) by using dispersion ( D )
showing a limited electron - conductivity. Examples thereof as such , as obtained from emulsion polymerization, ( iv ) by
may include : carbonaceous materials, such as carbon black , diluting dispersion (D ) with water, or through a combination
graphite fine powder and fiber, and fine powder and fiber of 60 of above techniques .
metals , such as nickel and aluminum . Generally, the composition ( AC ) is obtained by mixing :
The active substance for an electric double layer capacitor ( i ) dispersion (D ) , as above detailed , in an amount of from
may preferably comprise fine particles or fiber, such as 5 to 25 % wt ;
activated carbon , activated carbon fiber, silica or alumina ( ii ) at least one non - electroactive inorganic filler material ,
particles, having an average particle ( or fiber) diameter of 65 in an amount of from 70 to 95 % wt ;
0.05-100 um and a specific surface area of 100-3000 m² /g , ( iii ) one or more than one additional additive , in an
i.e. , having a relatively small particle (or fiber) diameter and amount of 0 to 5 % wt ; and
 US 10,968,362 B2
11 12
optionally, adding water for adjusting solid contents in the The invention is described hereunder in more detail with
range of 30 to 80 % wt , preferably 40 to 60 % wt . reference to the following example, which are provided with
The solid contents of the composition (AC ) is understood the purpose of merely illustrating the invention, with no
to be cumulative of all non -volatile ingredients thereof, intention to limit its scope .
notably including polymer ( A ) and non - electroactive inor- 5 Determination of Polar End Groups
ganic filler material. * H -NMR technique has been used for determination of
Still another object of the present invention is a method PIANCA end groups according to the technique described in
for the manufacture of a composite separator notably suit Journal , Maurizio , et al . End Groups in fluoropolymers.
able for use in an electrochemical cell , said method com this aim , about of Fluorine Chemistry. 1999 , vol. 95 , p . 71-84. To
prising the following steps: 10 20 mg of polymer were dissolved in 0.7 ml
(i ) providing a porous substrate; of hexadeuteroacetone . The ' H -NMR spectrum revealed
( ii ) providing an aqueous coating composition comprising to 14 Hz that is related ppm
notably a triplet at 3.78
to
with a J coupling F -H equal
-CH2 -OH end group .
dispersion (D ) , as above detailed , at least one non- electro Determination of Total Average Monomer (MA ) Content
active inorganic filler material and, optionally, at least one or Total average monomer (MA ) content in vinylidene fluo
more than one additional additive , i.e. the composition ( AC) , 15 ride ( VDF ) polymers was determined by acid-base titration .
as above detailed ; A sample of 1.0 g of polymer was dissolved in acetone at
(iii ) applying said composition (AC ) onto at least one a temperature of 70 ° C. Water ( 5 ml ) was then added
surface of said porous substrate to provide a coating com- dropwise under vigorous stirring so as to avoid coagulation
position layer; and of the polymer. Titration with aqueous NaOH having a
(iv ) drying said coating composition layer at a tempera- 20 concentration of 0.01 N until complete neutralization of
ture of at least 60 ° C. , to provide said composite separator. acidity was then carried out , with neutrality transition at
By the term “ separator” , it is hereby intended to denote a about -170 mV .
porous polymeric material which electrically and physically Determination of Melt Viscosity
separates electrodes of opposite polarities in an electro- Melt Viscosity (According to ASTM D3835 ) was mea
chemical cell and is permeable to ions flowing between 25 sured to demonstrate the improvement of molecular weight.
The test was performed in a Capillary Reomether Rheograph
them .
By the term “ electrochemical cell ” , it is hereby intended 2003 in a configuration ( L /D = 20 ) at 230 ° C. with a die
diameter of 1 mm . Measure of shear rate n (eta ) were
to denote an electrochemical cell comprising a positive performed at 100 sec - 1 .
electrode, a negative electrode and a liquid electrolyte ,
wherein a monolayer or multilayer separator is adhered to at 30 Example 1 — Manufacture of Aqueous
least one surface of one of said electrodes . VDF -HFP -AA Polymer Latex - Polymer A
Non - limitative examples of electrochemical cells include,
notably, batteries, preferably secondary batteries, and elec In a 21 It . horizontal reactor autoclave equipped with
tric double layer capacitors. baffles and stirrer working at 50 rpm , 13.5 It . of deionised
For the purpose of the present invention, by “ secondary 35 water were introduced . The temperature is brought to 80 ° C.
battery” it is intended to denote a rechargeable battery. and the pressure of 35 Bar ass was maintained constant
Non - limitative examples of secondary batteries include, throughout the whole trial by feeding VDF/ HFP gaseous
notably, alkaline or alkaline -earth secondary batteries . mixture monomers in a mol ration of 99 : 1 respectively . 250
The composite separator obtained from the method of the ml of a 100 g/l aqueous solution of ammonium persulfate
invention is advantageously an electrically insulating com- 40 (APS) were added over a period of 15 minutes ( 1 L /h ) then
posite separator suitable for use in an electrochemical cell . the solution of ammonium persulfate (APS ) was continu
In step ( iii ) of the method of the invention , the compo ously added at a flux rate of 60 ml/h for the whole duration
sition (AC ) is typically applied onto at least one surface of of the run ; in addition , 50 ml of a solution of acrylic acid
the porous substrate by a technique selected from casting, ( AA ) ( 50 g /l of acrylic acid in water) were fed every 250 g
spray coating, roll coating, doctor blading, slot die coating, 45 of monomers consumed .
gravure coating, ink jet printing, spin coating and screen When 4500 g of the mixture were fed, the feeding mixture
printing, brush , squeegee , foam applicator, curtain coating, was interrupted, then the pressure was let to fall down up to
vacuum coating 12 bar while keeping the reaction temperature constant.
Final reaction time was 223 min .
Non - limitative examples of suitable porous substrate The reactor was cooled to room temperature and latex was
include , notably, porous membranes made from inorganic, 50
organic and naturally occurring materials , and in particular
recovered . The VDF -HFP - AA polymer so obtained con
tained 98.3 % by moles of VDF, about 1.0 % by moles of HFP
made from nonwoven fibers ( cotton , polyamides , polyesters , and 0.7 % by moles of acrylic acid ( AA ) monomer .
glass ) , from polymers ( polyethylene, polypropylene, poly The aqueous latex so obtained had a solid content of
( tetrafluoroethylene), poly (vinyl chloride ), and from certain 24.8 % by weight. The VDF -HFP - AA polymer was dis
fibrous naturally occurring substances (e.g. asbestos ) . 55 persed in the aqueous latex under the form of particles
Advantageous results have been obtained when the having an average primary size of 243 nm , as measured
porous support was a polyolefin porous support, e.g. a according to ISO 13321 , was found to possess a melting
polyethylene or a polypropylene porous support. point of 153.6 ° C. (determined according to ASTM D3418 )
In step ( iv ) of the method of the invention , the coating a MV (230 ° C./100 sec- ? ) of 67 kPoise and a content of end
composition layer is dried preferably at a temperature com- 60 groups as follows: CF , H : 35 mmol/kg; CF , CHz: 19
prised between 60 ° C. and 200 ° C. , preferably between 70 ° mmol /kg; CH , OH : 8 mmol/kg.
C. and 180 ° C.
Should the disclosure of any patents, patent applications, Comparative Example 1 – Manufacture of Aqueous
and publications which are incorporated herein by reference VDF - AA Polymer Latex- Polymer A'
conflict with the description of the present application to the 65
extent that it may render a term unclear, the present descrip- In a 21 It . horizontal reactor autoclave equipped with
tion shall take precedence. baffles and stirrer working at 50 rpm , 13.5 It . of deionised
 US 10,968,362 B2
13 14
water were introduced . The temperature is brought to 90 ° C. mixture monomers in a molar ratio of 99 : 3 respectively . 250
and the pressure of 20 Bar ass was maintained constant ml of a 100 g/l aqueous solution of ammonium persulfate
throughout the whole trial by feeding VDF gaseous mono- ( APS ) were added over a period of 15 minutes ( 1 L /h ) and
mer. 15 ml of a 100 g/ l aqueous solution of ammonium at the same time 50 ml of a solution of acrylic acid ( AA ) ( 50
persulfate (APS ) were added over a period of 5 minutes (2005 g/l of acrylic acid in water) were fed every 250 g of polymer
ml/h ) and at the same time 22 ml of a solution of acrylic acid synthesized.
(AA ) (40 g/l of acrylic acid in water) were fed every 225 g After 30 minutes, the solution of APS was fed at a flux
of polymer synthesized . rate of 240 ml/h for the whole duration of the run .
After 30 minutes, additional amount of solution of APS When 4500 g of the mixture were fed, the feeding mixture
was added at a flux rate of 240 ml/ h for the whole duration 10 was interrupted , the pressure was let to fall down up to 12
of the run . When 4500 g of the mixture were fed , the feeding bar while keeping the reaction temperature constant. Final
mixture was interrupted, then the pressure was let to fall reaction time was 125 min .
down up to 12 bar while keeping the reaction temperature The reactor was cooled to room temperature, the latex was
constant. Final reaction time was 164 min . recovered . The VDF -HFP - AA polymer so obtained con
The reactor was cooled to room temperature and the latex 15 tained 96.13 % by moles of VDF, 2.97 % by moles of HFP
recovered . The VDF - AA polymer so obtained contained and 0.9 % by moles of acrylic acid ( AA ) monomer .
99.55 % by moles of VDF and 0.45 % by moles of acrylic The aqueous latex so obtained had a solid content of
acid (AA ) monomer. 25.4 % by weight. The VDF - HFP - AA polymer was dis
The aqueous latex so obtained had a solid content of persed in the aqueous latex under the form of particles
24.2 % by weight. The VDF -AA polymer was dispersed in 20 having an average primary size of 220 nm , as measured
the aqueous latex under the form of particles having an according to ISO 13321 , was found to possess a melting
average primary size of 189 nm , as measured according to point of 141 ° C. ( determined according to ASTM D3418 ) , a
ISO 13321 , was found to possess a melting point of 160 ° C. MV (230 ° C./100 sec - l ) of 22 kPoise .
(determined according to ASTM D3418 ) and a MV (230 ° 25
C./100 sec - l ) of 23 kPoise . Example 3 — Manufacture of Aqueous
VDF -HFP -AA Polymer Latex — Polymer C
Example 2 — Manufacture of Aqueous
VDF - HFP - AA Polymer Latex - Polymer B In a 21 It . horizontal reactor autoclave equipped with
baffles and stirrer working at 50 rpm , 13.5 It . of deionised
In a 21 It . horizontal reactor autoclave equipped with 30 water were introduced . The temperature was brought to 750
baffles and stirrer working at 50 rpm , 13.5 It . of deionised C. then HFP gaseous monomer is charge till obtain deltaP of
water were introduced . The temperature is brought to 75º C. 6.1 bar. The pressure of 35 bar was maintained constant
and the pressure of 35 Bar ass was maintained constant throughout the whole trial by feeding VDF/ HFP gaseous
throughout the whole trial by feeding VDF/ HFP gaseous mixture monomers in a molar ratio of 87.5 : 12.5 respectively.
mixture monomers in a mol ration of 99 : 3 respectively . 290 35 250 ml of a 100 g /l aqueous solution of ammonium persul
ml of a 100 g/l aqueous solution of ammonium persulfate fate (APS ) were added over a period of 15 minutes ( 1 L /h )
(APS ) were added over a period of 17 minutes ( 1 L /h ), and then continue to add the solution of ammonium persulfate
the solution of APS was then fed at a flux rate of 60 ml/ h for (APS ) with a flux rate of 60 ml/ h for the whole duration of
the whole duration of the run ; 50 ml of a solution of acrylic the trial together with 50 ml of a solution of acrylic acid
acid (AA ) ( 50 g /l of acrylic acid in water ) were fed every 40 (AA ) ( 50 g /l of acrylic acid in water) were fed every 250 g
250 g of monomers consumed . When 4500 g of the mixture of polymer synthesized.
were fed, the feeding mixture was interrupted, then the When 4500 g of the mixture were fed, the feeding mixture
pressure was let to fall down up to 12 bar while keeping the was interrupted , then the pressure was let to fall down up to
reaction temperature constant. Final reaction time was 318 12 bar while keeping the reaction temperature constant.
min . 45 Final reaction time was 326 min . The reactor was cooled to
The reactor was cooled to room temperature , the latex was room temperature, the latex was unloaded . The VDF -HFP
unloaded . The VDF -HFP -AA polymer so obtained con- AA polymer so obtained contained 86.72 % moles of VDF,
tained 96.13 % by moles of VDF, 2.97 % by moles of HFP 12.38 % moles of HFP and 0.9 % by moles of acrylic acid
and 0.9 % by moles of acrylic acid ( AA ) monomer . (AA ) monomer . The aqueous latex so obtained had a solid
The aqueous latex so obtained had a solid content of 50 content of 25.6 % by weight. The VDF -HFP - AA polymer
24.0 % by weight. The VDF -HFP - AA polymer was dis- was dispersed in the aqueous latex under the form of
persed in the aqueous latex under the form of particles particles having an average primary size of 273 nm , as
having an average primary size of 287 nm , as measured measured according to ISO 13321 , was found to possess a
according to ISO 13321 , was found to possess a melting melting point of 89 ° C. ( determined according to ASTM
point of 144 ° C. ( determined according to ASTM D3418 ) , a 55 D3418 ) , a MV (230 ° C./100 sec- ? ) of 48.6 kPoise , and a
MV (230 ° C./100 sec - ) of 31 kPoise , and a content of end content of end groups as follows: CF2H : 29 mmol /kg;
groups as follows: CF2H : 35 mmol/kg; CFz - CH3: 23 -CF2 - CHZ: 10 mmol/kg; -CH2OH : 7 mmol /kg.
mmol/kg; - CH2OH : 5 mmol /kg. Comparative Example 3 - Manufacture of Aqueous
Comparative Example 2 — Manufacture of Aqueous 60 VDF -HFP -AA Polymer Latex - Polymer C '
VDF - HFP - AA Polymer Latex - Polymer B '
In a 21 It . horizontal reactor autoclave equipped with
In a 21 It . horizontal reactor autoclave equipped with baffles and stirrer working at 50 rpm , 13.5 It . of deionised
baffles and stirrer working at 50 rpm , 13.5 It . of deionised water were introduced . The temperature was brought to 90 °
water were introduced . The temperature was brought to 90 ° 65 C. and the pressure of 30 Bar was maintained constant
C. and the pressure of 30 Bar ass was maintained constant throughout the whole trial by feeding VDF/ HFP gaseous
throughout the whole trial by feeding VDF/ HFP gaseous mixture monomers in a molar ratio of 87.5 : 12.5 respectively.
 US 10,968,362 B2
15 16
250 ml of a 100 g/l aqueous solution of ammonium persul- water were introduced . The temperature was brought to 90 °
fate ( APS ) were added over a period of 15 minutes ( 1 L / h ) C. then HFP gaseous monomer is charge till obtain deltaP of
and at the same time 50 ml of a solution of acrylic acid (AA ) 8.8 bar. The pressure of 30 Bar ass was maintained constant
( 50 g/l of acrylic acid in water ) were fed every 250 g of throughout the whole trial by feeding VDF/ HFP gaseous
polymer synthesized. 5 mixture monomers in a molar ratio of 78.5 :21.5 respectively.
After 30 minutes from the ignition restart to add the 250 ml of a 100 g /l aqueous solution of ammonium persul
solution of ammonium persulfate (APS ) with a flux rate of fate (APS ) were added over a period of 15 minutes ( 1 L /h )
240 ml/h for the whole duration of the trial. and at the same time 50 ml of a solution of acrylic acid (AA )
When 4500 g of the mixture were fed , the feeding mixture ( 50 g /l of acrylic acid in water) were fed every 250 g of
was interrupted, then the pressure was let to fall down up to 10 polymer synthesized .
12 bar while keeping the reaction temperature constant. After 30 minutes from the ignition restart to add the
Final reaction time was 141 min .
The reactor was cooled to room temperature, the latex was 240 ml/ hofforammonium
solution persulfate (APS ) with a flux rate of
the whole duration of the trial.
unloaded . The VDF - HFP - AA polymer so obtained con
tained 86.7 % moles of VDF, 12.4 % moles of HFP and 0.9 % 15 wasWhen 4500 g of the mixture were fed, the feeding mixture
interrupted , then the pressure was let to fall down up to
by moles of acrylic acid (AA ) monomer . The aqueous latex 12 bar while keeping
so obtained had a solid content of 23.8 % by weight. The Final reaction time was the reaction temperature constant.
VDF -HFP - AA polymer was dispersed in the aqueous latex room temperature, the latex min 285 . The reactor was cooled to
was unloaded . The VDF -HFP
under the form of particles having an average primary size
of 340 nm , as measured according to ISO 13321, was found 20 AA polymer so obtained contained 77.8 % by moles of VDF,
to possess a melting point of81.2° C . (determined according 21.3 % by moles of HFP and 0.9% by moles of acrylic acid
to ASTM D3418 ) and a MV (230 ° C./100 sec- ? ) of 14 ( AA ) monomer .
kPoise . The aqueous latex so obtained had a solid content of 24 %
by weight. The VDF -HFP - AA polymer was dispersed in the
Comparative Example 4Manufacture of Aqueous 25 aqueous latex under the form of particles having an average
VDF -HFP -AA Polymer Latex - Polymer D ' primary size of 285 nm , as measured according to ISO
13321 , was found to possess a possess a Tg= -15.9 ° C.
In a 21 It . horizontal reactor autoclave equipped with ( determined according to ASTM D3418 ) , a MV (230 °
baffles and stirrer working at 50 rpm , 13.5 It . of deionised C./100 sec- ? ) of 23 kPoise and Mooney ( ( 1 + 10 ' ) @ 121 ° C. )
water were introduced . The temperature was brought to 90 ° 30 of 63.3 , and a content of end groups as follows: CF2H : 68
C. then HFP gaseous monomer is charge till obtain deltaP of mmol/kg ; - CF2CH3: 15 mmol/kg ; CH , OH : 38 mmol /
10.6 bar. The pressure of 35 bar was maintained constant
throughout the whole trial by feeding VDF / HFP gaseous kgProperties .
of the latexes are summarized in Table 1 herein
mixture monomers in a mol ration of 78.5 :21.5 respectively. below :
220 ml of a 100 g/l aqueous solution of ammonium persul- 35
fate ( APS ) were added over a period of 13 minutes ( 1 L /h ) TABLE 1
then continue to add the solution of ammonium persulfate
(APS ) with a flux rate of 60 ml/ h for the whole duration of VDF/ HFP MV (kPoise)
the trial together with 50 ml of a solution of acrylic acid Ex . Polymers mol : mol Tmºc. @ 100 sec
( AA ) ( 50 g/l of acrylic acid in water ) were fed every 250 g 40 Ex . 1 A 99 : 1 153.6 67
of polymer synthesized. Ex . 1C A' 100 : 0 160.0 23
The temperature of polymerization was reduced to 75º C. ExEx .. 22C BB ' 97 : 3 144.0 31
after 450 g of conversion . 97 : 3 140.0 22
49
When 4500 g of the mixture were fed , the feeding mixture ExEx.. 33C 87.5 : 12.5
87.5 : 12.5
89.0
81.2 14
was interrupted, then the pressure was let to fall down up to 45 Ex . 4C D ' 78.5 : 21.5 (*)Tg = -21.1 40
12 bar while keeping the reaction temperature constant. Ex . 5C D" 78.5 : 21.5 ( * ) T, = -15.9 23
Final reaction time was 269 min .
The reactor was cooled to room temperature , the latex was ( * )no detectable melting point
unloaded . The VDF -HFP - AA polymer so obtained con Preparation of Coated Separators
tained 77.8 % by moles of VDF, 21.3 % by moles of HFP and 50 Emulsion polymers were used as binders for ceramic
0.9 % by moles of acrylic acid ( AA ) monomer.
The aqueous latex so obtained had a solid content of particles polyolefin
to create high temperature resistant coatings on
porous support so as to provide for composite
25.7 % by weight. The VDF -HFP -AA polymer was dis separators for Li -ion batteries. A first mixture consisting of
persed in the aqueous latex under the form of particles
having an average primary size of 292 nm , as measured 55 872 wtwt%%ofofsurfactant alumina CR6 from Baikowski, 10 wt % of latex,
( sodium dodecyl sulphate, SDS ) and 1
according to ISO 13321 , was found to possess a Tg = -21.1 ° wt % of antifoam BYK - 023 was prepared. Then water was
C. (determined according to ASTM D3418 ) , a MV (230 °
C./100 sec - 1 ) of 40 kPoise and Mooney ( ( 1 + 10 ' ) @ 121 ° C. ) added to the said mixture until achieving 50 wt % of solid
of 158.1 , and a content of end groups as follows: CF H : content in the slurry , and the slurry was mixed at 1000 rpm
25 mmol/kg ; CF2CH3: 37 mmol/kg; _CH , OH: 7 60 for 20 min by using a planetary mixing system . Subse
mmol/kg. quently, the prescribed amount of VDF polymer latex was
added to the aqueous slurry and the resulting mixture was
Comparative Example 5 — Manufacture of Aqueous mixed further for 2-10 min at 1000 rpm . The coating
VDF -HFP -AA Polymer Latex - Polymer D " composition so obtained was casted on a porous polyolefin
65 substrate using a casting knife set at 30 um of blade height.
In a 21 It . horizontal reactor autoclave equipped with The coated separator was obtained by drying at a tempera
baffles and stirrer working at 50 rpm , 13.5 It . of deionised ture of 70 ° C. in a ventilated oven for 30 minutes.
 US 10,968,362 B2
17 18
Dry Lamination The circular polymeric samples ( o = 25 mm ; 1.5 mm thick )
The separator is laminated at cathode without the addition were dried at 55 ° C. overnight and then immersed in EC
of any solvent. The cathode used was obtained from a ( ethylene carbonate ):DMC ( dimethyl carbonate ) 1 : 1 mix
composition comprising 2 % wt of SOLEF (R) PVDF 5130 ture, after measuring the dry weight and dry thickness. The
(polymer binder ), 3 % wt of Carbon Black Super C65 by
5
weight was measured at different time intervals from immer
Imerys ( electron conductive agent) and 95 % wt of Lithium sion into the swelling agent till the maximum uptake was
Cobalt Oxide D10 from Umicore ( cathode active material), reached . Results are summarized below :
and possessed a porosity of 40 % . Lamination of the sepa TABLE 4
rator onto the cathode surface was performed using a 10
hydraulic flat press operating in the following conditions of Polymers Wt increase (%)
pressure , time and temperature: 50 MPa , 15 min and 70 ° C. B' 129 + 7
After lamination the adhesion strength was evaluated apply B 130 + 14
ing a peeling test at an angle of 180 ° and at a delamination D" dissolution
speed of 10 mm /min following ASTM D903 standard . 15 D' dissolution

TABLE 2
Excessive swelling or dissolution occurs for materials D '
Polymers Adhesion ( N /m )
and D " of comparison .
20
B' 0.3 + 0.1
The invention claimed is :
0.8 + 0.1 1. An aqueous dispersion ( D ) comprising particles of
C' 1.8 + 0.4 polymer (A) , wherein polymer ( A ) is a vinylidene fluoride
go
to
e ( VDF ) copolymer comprising recurring units derived from
3.0 + 0.4 25
D" 3.9 + 1
vinylidene fluoride (VDF ) monomer and recurring units
D' 8.8 + 1.3
derived from at least one hydrophilic (meth )acrylic mono
mer (MA ) of formula :
30
Characterization of Composite Separator: Wet Adhesion R2 R3
Post 48 h in EC : DMC
Wet lamination is the evaluation of the wet adhesion of R1 R
the separator to cathode with the addition of alkyl carbonate OH
mixture solvent. The coated separators prepared as above 35
detailed and the same cathode as above detailed , under the
form of specimens having dimensions of 11 cmx8 cm , were wherein each of R1 , R2 , R3 , equal or different from each
pre -conditioned by drying at 55 ° C. overnight. 500 ul of a other, is independently a hydrogen atom or a C , -C3
mixture of ethylene carbonate ( EC ) and propylene carbonate hydrocarbon group , and Ron is a hydroxyl group or a
( PC ) EC : DMC 1 : 1 were poured on cathode surface and the 40 C -C hydrocarbon moiety comprising at least one
separator is laid on top of it . The cathode -separator assembly hydroxyl group , said polymer (A)
was closed in vacuum in a coffee bag within 2 PTFE sheets ( i ) comprising more than 85.0 % moles of recurring units
and then pressed with a flat hydraulic press at 85 ° C. , 1 MPa , derived from VDF and from 0.05 to 10 % by moles of
5 min . Soon after opening the coffee bag the separator was recurring units derived from said hydrophilic (meth )
peeled off from the cathode with a peeling angle of 180 ° at 45 acrylic monomer (MA ), with respect to the total num
a peeling rate of 10 mm /min following ASTM D903 . Results ber of recurring units of polymer (A) ;
are summarized in the following Table.
( ii ) possessing a melt viscosity of at least 30 kPoise, when
TABLE 3 50
determined at a shear rate of 100 sec- ?, and at a
Polymers Adhesion ( N / m )
temperature of 230 ° C. , according to ASTM D3835 ,
and
B'
B
11.5 + 1.0
21.6 + 1.4
( iii ) possessing an amount of end groups of formula
CH2 - OH of at least 5 mmol /kg and at most 20
55 mmol/kg ;
Swelling wherein said dispersion is substantially free from fluori
The swelling of polymers was evaluated by measuring the nated surfactants ; and
increase in weight of molded polymeric samples after wherein the particles of polymer ( A ) comprise a primary
immersion into a carbonate mixture. The molded specimens 60 particle average size of less than 1 um as measured
were obtained by compression molding, by loading the according to ISO13321.
polymeric powder of coagulated lattice directly into the 2. The dispersion ( D ) of claim 1 , wherein polymer (A)
stainless steel frame of a flat press . The stainless steel frame consists essentially of recurring units derived from VDF, and
used was designed to obtain 5 circular samples with diam from monomer (MA) .
eter of 25 mm and thickness of 1.5 mm . The samples were 65 3. The dispersion ( D ) of claim 1 , wherein polymer ( A )
obtained by melting the polymer at Tm + 60 ° C. and then consists essentially of recurring units derived from VDF,
cooling at room temperature . from HFP and from monomer (MA ).
 US 10,968,362 B2
19 20
4. The dispersion ( D ) of anyone of the preceding claims , 9. A method of making the dispersion ( D ) of claim 1 , said
wherein the hydrophilic (meth )acrylic monomer (MA ) com- method comprising emulsion polymerizing VDF and said
plies formula : hydrophilic (meth ) acrylic monomer (MA ) in the presence of
a persulfate inorganic initiator, at a temperature of at most
R2 R3 5 80 ° C. , under a pressure of at least 20 bar, without adding
any fluorinated surfactant.
10. An aqueous electrode- forming composition compris
R1 R ing the dispersion (D ) according to claim 1 , a powdery
OH electrode material, and, optionally an electroconductivity
10
imparting additive and / or a viscosity modifying agent.
11. An aqueous coating composition (AC ) comprising
wherein each of R1 , R2 , equal or different from each dispersion ( D ) according to claim 1 , at least one non
other, is independently an hydrogen atom or a C , -CZ electroactive inorganic filler material and , optionally , one or
hydrocarbon group , and R3 is hydrogen and RoH is a more than one additional additive .
hydroxyl group or a C , -C hydrocarbon moiety com- 15 12. The composition (AC ) of claim 11 , wherein the
prising at least one hydroxyl group.
5. The dispersion (D ) of claim 4 , wherein the monomer non - electroactive inorganic filler material is selected from
the group consisting of natural and synthetic silicas , zeolites ,
(MAhydroxyethylacrylate
) is selected from the(HEA
group consisting of:
) of formula : aluminas , titanias, metal carbonates , zorconias, silicon phos
phates and silicates .
20
13. The composition (AC) of claim 11 , wherein the
H

?. you
H

OH

2 -hydroxypropyl acrylate (HPA ) of either of formulae:

25
composition includes at least one additional additive
selected from the group consisting of viscosity modifiers,
anti- foams, and non - fluorinated surfactants, and anionic
surfactants .
14. The composition ( AC ) according to claim 11 , said
composition ( AC ) being obtained by:
mixing:
( i ) dispersion ( D ) in an amount of from 5 to 25 % wt ;
( ii ) at least one non - electroactive inorganic filler material ,

yete
30
in an amount of from 70 to 95 % wt ; and
( iii ) one or more than one additional additive , in an
amount of 0 to 5 % wt ; and optionally, adding water for
H adjusting solid contents in the range of 30 to 80% wt.
35
15. A method for the manufacture of a composite sepa
rator suitable for use in an electrochemical cell , said method
CH3 ?? comprising:
CH3
applying the composition ( AC ) as defined in claim 11
onto at least one surface of a porous substrate to
provide a coating composition layer, and
acrylic acid (AA ) of formula : 40
drying said coating composition layer at a temperature of
at least 60 ° C. , to provide said composite separator.

and mixtures thereof.

yle OH
45

50
16. The dispersion (D ) of claim 4 , wherein each of R1 , R2 ,
R3 are hydrogen , and Roh is a hydroxyl group or a C1 - C5
hydrocarbon moiety comprising at least one hydroxyl group .
17. The dispersion (D ) of claim 6 , wherein polymer (A)
comprises at least 0.2 % moles and at most 3 % moles of
recurring units derived from said hydrophilic (meth )acrylic
monomer (MA) .
18. The dispersion (D) according to claim 7, wherein
6. The dispersion ( D ) of claim 1 , wherein polymer (A) polymer (A) possesses a melt viscosity (MV) of less than 80
comprises at least 0.1 , % moles of recurring units derived kPoise , when determined at a shear rate of 100 sec - 1 , and at
from said hydrophilic (meth ) acrylic monomer (MA ) and / or a temperature of 230 ° C. , according to ASTM D3835 .
polymer ( A ) comprises at most 7.5 % moles of recurring 19. The dispersion (D ) according to claim 8 , wherein
polymer ( A ) comprises an amount of polar end groups of
units
(MA )derived
. from said hydrophilic ( meth )acrylic monomer 55 mmol
formula/kg. CH ,OH of at least 5 mmol/kg and at most 12
7. The dispersion ( D ) according to claim 1 , wherein 20. The composition (AC ) of claim 13 , wherein the at
polymer (A) possesses a melt viscosity (MV) of no more least one additional additive is selected from the group
than 100 kPoise when determined at a shear rate of 100
sec - 1 , and at a temperature of 230 ° C. , according to ASTM consisting of non - ionic emulsifiers, alkoxylated alcohols,
D3835 .
60
ethoxylated alcohols , propoxylated alcohols, mixed ethoxy
8. The dispersion ( D ) according to claim 1 , wherein lated /propoxylated alcohols , fatty acid salts , alkyl sulfonate
polymer ( A ) comprises an amount of polar end groups of salts , sodium dodecyl sulfate, alkylaryl sulfonate salts and
formula CH , OH of at least 5 mmol/kg and at most 18 arylalkyl sulfonate salts .
mmol/kg.