CN117050237A - 一种溶液型粘结剂及其制备方法和用途 - Google Patents
一种溶液型粘结剂及其制备方法和用途 Download PDFInfo
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- CN117050237A CN117050237A CN202311159605.0A CN202311159605A CN117050237A CN 117050237 A CN117050237 A CN 117050237A CN 202311159605 A CN202311159605 A CN 202311159605A CN 117050237 A CN117050237 A CN 117050237A
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- monomer
- acid
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- nitrile
- monomers
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- 239000011230 binding agent Substances 0.000 title claims abstract description 36
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- 239000000178 monomer Substances 0.000 claims abstract description 92
- 239000000839 emulsion Substances 0.000 claims abstract description 23
- 150000002825 nitriles Chemical class 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- 239000000853 adhesive Substances 0.000 claims abstract description 13
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- 239000003513 alkali Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 14
- -1 N-methacrylamide Chemical compound 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
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- 239000003999 initiator Substances 0.000 claims description 12
- 150000001408 amides Chemical class 0.000 claims description 10
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
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- 230000001105 regulatory effect Effects 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 125000005336 allyloxy group Chemical group 0.000 claims description 3
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims description 2
- ZEMHQYNMVKDBFJ-UHFFFAOYSA-N n-(3-hydroxypropyl)prop-2-enamide Chemical compound OCCCNC(=O)C=C ZEMHQYNMVKDBFJ-UHFFFAOYSA-N 0.000 claims description 2
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 claims description 2
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical class OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 2
- 150000007513 acids Chemical class 0.000 claims 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- LUIGSJYSMIUMPK-UHFFFAOYSA-N propane-1-sulfonoperoxoic acid Chemical compound CCCS(=O)(=O)OO LUIGSJYSMIUMPK-UHFFFAOYSA-N 0.000 claims 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
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- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 238000010899 nucleation Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
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- 235000010350 erythorbic acid Nutrition 0.000 description 2
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- 229940026239 isoascorbic acid Drugs 0.000 description 2
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
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Abstract
本发明公开一种溶液型粘结剂及其制备方法和用途。所述粘结剂的制备主要包括如下步骤：首先，由丙烯酸烷基酯单体、腈基单体和功能单体酸经乳液聚合制备得到乳胶粒子。乳胶粒子粒径均一且富含极性官能团，可作为沉淀聚合的种子。以腈基单体、功能单体酸和丙烯酰胺等为沉淀聚合单体，反应生成的低聚物在氢键和疏水作用下沉积在种子聚合物表面，形成沉淀颗粒。再通过碱液中和得到溶液型粘结剂。本发明提供的溶液型粘结剂适用于锂离子电池负极，具有粘结强度高、电解液溶胀度低和一定的加工柔韧性，且制备工艺简单、批次稳定性好。
Description
技术领域
本发明属于高分子材料技术领域，具体涉及粘结剂，尤其涉及一种用于锂离子电池负极的溶液型粘结剂。
背景技术
负极粘结剂是锂离子电池中的一种重要高分子材料，其主要作用是将负极活性物质(石墨、硅碳、硅等)和导电剂等粘附在集流体上。虽然粘结剂用量不是很多(约占负极材料的1.5-5％)，但其性能的优劣对于锂电池性能如比容量、库伦效率、内阻和循环寿命等均有重要影响。
目前，应用最为广泛的负极粘结剂是丁苯橡胶乳液(SBR)，其在使用过程中需加入羧甲基纤维素(CMC)作为增稠剂和分散剂。材料组成决定SBR/CMC所含有的羧基、酯基和腈基等极性官能团含量有限，同负极材料特别是硅碳负极间作用力较弱，因而电池综合性能特别是低温性能已日渐难以满足应用要求。聚丙烯酸类粘结剂因聚合物含有高含量的极性官能团，在充放电过程中，极性官能团同锂离子间存在络合与解络合作用，可促进锂离子传导降低电池内阻。此外，聚丙烯酸类粘结剂与硅负极表面可形成氢键作用，提高对负极材料的分散和粘附，从而抑制负极活性物质在充放电过程中的体积膨胀，改善SEI膜的性能以防止电化学循环过程中电解液的分解。
CN109777328B公开了一种锂离子电池负极水性粘结剂，是将硬单体、软单体、功能性单体、酸性单体和交联剂经乳液聚合制备得到，该粘结剂能够保持良好吸液率、粘结力和充放电性能。CN111057184A公开了一种负极极片水性粘结剂的制备方法，采用无皂乳液聚合的方法，通过亲水单体、亲油单体和功能性单体共聚，降低水性粘结剂表面张力，分散时间短，可提高负极极片的生产效率。上述方法所制备的乳液型聚丙烯酸类粘结剂，通常含有较高比例的亲电解液组分如丙烯酸酯类，其在电解液中的溶胀度较高，因而极片反弹较大，高温循环性能也较差。
CN111500228B公开了一种溶液型电池用聚丙烯酸类粘合剂，该粘结剂为同时带有亲水和疏水单元的聚合物，其在水中为沉淀，加入碱液后变为盐溶解在水中。所制备的粘结剂聚合物中，中低分子量聚合物占聚合物总量的5wt％以下(所述中低分子量聚合物的分子量小于或等于10万)，具有较强的粘结力。基于沉淀聚合所制备的溶液型粘结剂具有分子量大、低聚物残留少等特性，应用于锂离子电池负极具有粘结强度高、循环性好等优点。但常规的沉淀聚合要求所用聚合单体在溶剂中具有较好的溶解性，而所生成的共聚物在溶剂中溶解性较低，链长达到临界值之后可析出成核生成沉淀。因而聚合单体的种类及加入量具有较大局限性，常用的共聚单体如丙烯酸、丙烯酰胺和丙烯腈等，难以实现粘结强度以及极片柔韧性能的平衡，产品性能仍需进一步提升。此外，搅拌和温度等因素极易对沉淀聚合的成核过程产生影响，从而引起最终产物分子量的巨大波动，产品批次稳定性面临巨大挑战。
发明内容
为了解决以上技术问题，本发明提供一种溶液型粘结剂及其制备方法和用途。采用水相种子沉淀聚合工艺制备溶液型粘结剂。首先，由丙烯酸烷基酯单体、腈基单体和功能单体酸经乳液聚合制备得到乳胶粒子。乳胶粒子粒径均一且富含极性官能团，可作为沉淀聚合的种子。以腈基单体、功能单体酸和丙烯酰胺等为沉淀聚合单体，反应生成的低聚物在氢键和疏水作用下沉积在种子聚合物表面，最终形成沉淀颗粒。可通过改变加入的种子类型及含量对沉淀聚合物颗粒形貌、尺寸进行调控，提高了沉淀聚合工艺稳定性。并借助种子赋予产品多功能性，如以低玻璃化转变温度的共聚物粒子为种子可提高负极粘结剂的柔韧性。
为实现上述目的，本发明所采用的技术方案如下：
一种溶液型粘结剂的制备方法，包括以下步骤：
1)将乳化剂和水加入反应釜内打底，开启搅拌并加热至设定温度；
2)将乳化剂、水、丙烯酸烷基酯单体、腈基单体和功能单体酸加入釜一中进行预乳化，得到种子预乳化液；
3)将去离子水、腈基单体、功能单体酸和酰胺类单体加入釜二中混合均匀，得到壳层单体混合液；
4)将种子预乳化液与引发剂溶液同步滴入反应釜内，滴加时间为0.5-1小时，滴加结束后继续保温15-30min；
5)将反应釜内温度调至设定温度后，同步滴加壳层单体混合液与引发剂溶液，滴加时间为2-4小时，待滴加结束后，继续保温1-2小时；
6)待反应体系温度降至室温后，收集聚合物沉淀并将其分散在去离子水中；
7)将步骤6)所得分散液升温至70-90℃，并加入碱液调节pH为7-8，待pH稳定后继续保温1-2小时，降温出料得到溶液型粘结剂。
在一项优选的实施方案中，所述种子预乳化液，按照原料的质量比计，包含乳化剂0.1-0.9％、水20-30％、丙烯酸烷基酯单体35-50％、腈基单体10-20％、功能单体酸15-25％。
在一项优选的实施方案中，所述壳层单体混合液，按照原料的质量比计，包含水20-30％、酰胺类单体10-40％，腈基单体20-50％，功能单体酸15-30％。
在一项优选的实施方案中，所述种子预乳化液中单体(包含丙烯酸烷基酯单体、腈基单体、功能单体酸)与壳层单体混合液中单体(包含酰胺类单体、腈基单体、功能单体酸)的质量比为(2-30):(70-95)。
在一项优选的实施方案中，所述丙烯酸烷基酯单体为(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸十二烷基酯中的至少一种。
在一项优选的实施方案中，所述腈基单体选自丙烯腈和/或甲基丙烯腈。
在一项优选的实施方案中，所述功能单体酸选自丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、富马酸和马来酸中的至少一种，优选甲基丙烯酸。
在一项优选的实施方案中，所述酰胺类单体选自丙烯酰胺、N-甲基丙烯酰胺、N-乙基丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二乙基丙烯酰胺、2-甲基丙烯酰胺、N-羟甲基丙烯酰胺、N-羟乙基丙烯酰胺、N-羟丙基丙烯酰胺中的至少一种，优选丙烯酰胺。
优选地，所述乳化剂选自至少含有一个烯属不饱和官能团的表面活性剂，优选选自烯丙氧基异构醇醚硫酸酯氨盐、烯丙基聚醚磷酸酯、含烯丙基的特种硫醇硫酸盐、烯丙基聚氧化烯醚硫酸酯盐、烯丙基烷基琥珀酸酯磺酸酯盐、烯丙基醚羟基丙磺酸酯盐、聚氧乙烯苯乙烯化苯基醚硫酸酯盐中的至少一种。合适的例子包括但不限于艾迪科SR-10(烯丙氧基异构醇醚硫酸酯氨盐)、上海忠诚精细化工的V-100P(烯丙基聚醚磷酸酯乳化剂)。
优选地，所述引发剂为有机过氧化物引发剂、无机过氧化物引发剂和氧化还原引发剂中的一种或多种，优选自过硫酸铵、过硫酸钠、过硫酸钾、过硫酸铵与异抗坏血酸、双氧水与亚硫酸氢钠中的至少一种。
优选地，所述引发剂的总用量占丙烯酸烷基酯单体、功能单体酸、腈基单体、酰胺类单体质量和的0.01-2％，优选0.1-0.5％。
优选地，所述中和剂为无机碱金属氢氧化物和无机金属碳酸盐中的一种或多种，优选氢氧化钠、氢氧化锂、碳酸钠中的一种或多种。
优选地，制备过程中水的添加量以聚合产物固含量达到10-40％，优选15-30％为准，溶液型粘结剂固含量达到1-15％，优选3-8％。
在一项优选的实施方案中，步骤1)中设定温度为75-90℃。
在一项优选的实施方案中，步骤5)中设定温度为25-80℃。
本发明还提供一种如前文所述的制备方法制得的溶液型粘结剂在锂离子电池负极极片中的应用。所述溶液型粘结剂适用于人造石墨、天然石墨、硬碳、硅、硅碳等负极活性材料，可以采用本领域公知的方法制备负极极片并组装得到锂离子电池。
本发明具有如下有益效果：
(1)本发明采用种子沉淀聚合工艺，首先由乳液聚合制备得到富含极性官能团的乳胶粒子，进而将其作为种子，以腈基单体、羧酸单体和酰胺类单体为共聚单体，反应生成的低聚物在氢键和疏水作用下沉积在聚合物种子表面，最终形成沉淀颗粒。种子数目、粒径可控，提高了沉淀聚合工艺稳定性。
(2)本发明的溶液型粘结剂，包含乳液聚合所得种子共聚物与沉淀聚合所得壳层共聚物。种子共聚物含有大量丙烯酸酯类单体，具有良好的电解液亲和力，可降低锂离子电池内阻，且玻璃化转变温度较低，可改善极片柔韧性。而沉淀聚合所得壳层共聚物分子量大，富含极性官能团，可提高粘结力，抑制极片反弹。
(3)本发明的溶液型粘结剂富含羧基基团，羧基基团的存在提高了聚合物同负极活性物质、导电剂及分散剂间的相互作用，有利于浆料稳定分散。此外，大量羧基基团使得聚合物具有较强的增稠作用，可减少浆料制备过程中增稠剂的加入量。
(4)本发明种子制备过程中所使用的乳化剂为至少含有一个烯属不饱和官能团的表面活性剂，可参与聚合并接枝到聚合物上，为乳胶粒子提供良好的胶体稳定性，同时减少小分子物质的残留，有效提高锂离子电池的电化学稳定性。
(5)本发明的溶液型粘结剂富含腈基和酰胺基团，共聚物间可形成较强的氢键作用，可提高粘结剂与负极活性物质及集流体间的作用力；此外，极性官能团同锂离子间存在络合与解络合作用，可促进锂离子传导降低电池内阻。
具体实施方式
下面通过具体实施例对本发明做进一步说明，本发明所述实施例只是作为对本发明的说明，不限制本发明的范围。
实施例及对比例中主要原料及来源如表1所示：
表1、主要原料及来源
如无特殊说明，各实施例中所用到的其它化学试剂均为从市场购买得到，纯度为分析纯。
本发明以下实施例采用的测试方法如下：
浆料分散性评测：观察所制备的负极极片烘烤后的外观，包括极片开裂、卷曲、黑斑和凹坑情况。
电解液溶胀评测：将粘结剂乳液在50℃烘箱内干燥成膜，取质量为M1的膜片。将膜片浸泡入电解液中并置于60℃烘箱内保温48小时，利用滤纸擦干膜片表面的电解液，称重为M2。电解液溶胀度＝(M2-M1)/M1×100％。
剥离强度评测：剥离强度的测试方法参照美国材料与试验协会标准ASTM D3330，所用设备为电脑式拉力试验机(KJ-1065)。
如无特殊说明，各实施例中原料“份”数均指代“质量份”。
实施例1
(1)将0.03份SR-10、1400份去离子水加入到反应釜内，开启搅拌设定转速为200r/min，鼓入氮气驱氧并加热至85℃；
(2)将0.2份SR-10、8份去离子水、10份EHA、5份AN和5份MAA依次加入预乳化釜一中并开启搅拌，得到种子预乳化液；
(3)将90份去离子水、60份AA、60份AM和90份AN加入混合釜二中并开启搅拌，得到壳层单体混合液；
(4)同步滴加种子预乳化液与APS溶液(0.3份APS溶解于10份去离子水中)，控制滴加时间为1小时，待滴加结束后继续保温30min；
(5)将反应釜内温度调整至50℃，待温度稳定后，开始同步滴加壳层单体混合液与预先配置好的引发剂溶液(氧化剂为0.3份APS溶解于40份去离子水中，还原剂为0.15份IAA异抗坏血酸溶解于40份去离子水中)，控制滴加时间为3小时，待滴加结束后继续保温2小时；
(6)待反应釜内温度降至室温后，过滤收集聚合物沉淀并将其分散在4000份去离子水中；
(7)将沉淀物颗粒分散液升温至80℃，待温度稳定后加入中和剂氢氧化锂溶液(质量浓度为15％)调节pH约为8.0，待pH稳定后继续保温1.5小时，降温至室温后，过滤出料得到溶液型粘结剂。
实施例2-8
采用与实施例1基本相同的方法制备乳液型粘结剂，区别只是根据表2改变所用各原料的选型和用量。
实施例9
采用实施例1方法制备溶液型粘结剂，区别在于对以下原料及操作步骤进行调整：原料中将所用引发剂由APS改为过硫酸钾；操作步骤(1)中反应釜温度改为75℃；步骤(4)中滴加时间为30分钟，保温时间为15分钟；步骤(5)中控制壳层单体混合液与引发剂溶液滴加时间为2小时，保温时间为1小时；步骤(7)中控制中和温度为70℃，待pH稳定后继续保温2小时。
实施例10
采用实施例1方法与原料制备溶液型粘结剂，区别在于对以下原料及操作步骤进行调整：原料中将所用引发剂由APS改为过硫酸钠；操作步骤(1)中反应釜温度改为90℃；步骤(4)中滴加时间为45分钟，保温时间为20分钟；步骤(5)中控制壳层单体混合液与引发剂溶液滴加时间为4小时，保温时间为1.5小时；步骤(7)中控制中和温度为90℃，待pH稳定后继续保温1小时。
对比例1
与实施例1方法相比，(1)、(2)、(4)步省略，从第(3)步配制壳层单体水溶液，然后直接从第(5)步开始制备壳层硬单体粘结剂。
对比例2
与实施例1方法相比，只执行步骤(1)、(2)、(4)，不加壳层硬单体，得到乳液型粘结剂。
对比例3
与实施例1方法相比，区别在于使用SDS代替SR-10。
将实施例与对比例所制备的乳液型粘结剂应用于锂离子电池负极极片的制备，具体步骤如下：
(1)浆料制备：室温下将0.5份的羧甲基纤维素钠(CMC)加入到100份的去离子水，高速搅拌约二十分钟，然后分别加入1份的炭黑导电剂(Super P)、96.5份的负极活性物质(石墨)和2份的溶液型粘结剂，每种材料加入后均高速搅拌约十分钟以混合均匀，经100目滤网过滤后得到负极浆料。
(2)极片涂布：将制备的负极浆料均匀涂布于集流体(铜箔)上，涂布厚度为100μm，置于80℃烘箱内干燥5分钟，在室温下经辊压机辊压后得到厚度为70μm的负极极片。
对制备的各乳液型粘结剂进行电解液溶胀测试，对所制备的负极极片分别进行浆料分散性、剥离强度和电化学性能评测，测试结果如表3所示。
从表3中性能结果可以看出，与对比例1相比，利用实施例1-10所得粘结剂制备的浆料具有较好的分散性能、极片具有较好的柔韧性，这是因为核层由乳液聚合制备的共聚物富含丙烯酸酯类单体其玻璃化转变温度较低有利于改善柔韧性，而未采用种子乳液制备的粘结剂出现开裂情况，表明其加工性存在问题。与对比例2相比，利用实施例1-10所得粘结剂制备的膜片具有较低的电解液溶胀度，所制备的极片剥离强度更大，这是因为壳层由沉淀聚合制备得到的共聚物分子量大，且富含极性官能团，分子间可形成较好的氢键作用，因而具有较好的耐电解液性能，且剥离强度高。与对比例3相比，实施例采用的反应型乳化剂具有粘接力高和电解液溶胀低的特点，这是由于SDS乳化剂会游离在粘结剂中，遇到电解液浸泡发生迁移，乳胶粒的形态保持存在困难，粘接力也会下降。
表2、实施例、对比例中各原料质量份
表3、性能测试结果
| 性能 | 浆料分散性 | 极片成膜情况 | 电解液溶胀度/％ | 剥离强度/(N/m) |
| 实施例1 | 正常 | 未开裂 | 15 | 11.0 |
| 实施例2 | 正常 | 未开裂 | 20 | 10.8 |
| 实施例3 | 正常 | 未开裂 | 12 | 11.0 |
| 实施例4 | 正常 | 未开裂 | 18 | 11.2 |
| 实施例5 | 正常 | 未开裂 | 12 | 12.8 |
| 实施例6 | 正常 | 未开裂 | 15 | 13.5 |
| 实施例7 | 正常 | 未开裂 | 18 | 11.7 |
| 实施例8 | 正常 | 未开裂 | 12 | 12.9 |
| 实施例9 | 正常 | 未开裂 | 11 | 11.6 |
| 实施例10 | 正常 | 未开裂 | 16 | 12.3 |
| 对比例1 | 颗粒 | 开裂 | 8 | 13.0 |
| 对比例2 | 正常 | 未开裂 | 40 | 6.5 |
| 对比例3 | 正常 | 未开裂 | 59 | 7.2 |
Claims (10)
1.一种溶液型粘结剂的制备方法，包括以下步骤：
1)将乳化剂和水加入反应釜内打底，开启搅拌并加热至设定温度；
2)将乳化剂、水、丙烯酸烷基酯单体、腈基单体和功能单体酸加入釜一中进行预乳化，得到种子预乳化液；
3)将去离子水、腈基单体、功能单体酸和酰胺类单体加入釜二中混合均匀，得到壳层单体混合液；
4)将种子预乳化液与引发剂溶液同步滴入反应釜内，滴加时间为0.5-1小时，滴加结束后继续保温15-30min；
5)将反应釜内温度调至设定温度后，同步滴加壳层单体混合液与引发剂溶液，滴加时间为2-4小时，待滴加结束后，继续保温1-2小时；
6)待反应体系温度降至室温后，收集聚合物沉淀并将其分散在去离子水中；
7)将步骤6)所得分散液升温至70-90℃，并加入碱液调节pH为7-8，待pH稳定后继续保温1-2小时，降温出料得到溶液型粘结剂。
2.根据权利要求1所述的方法，其特征在于，所述种子预乳化液，按照原料的质量比计，包含乳化剂0.1-0.9％、水20-30％、丙烯酸烷基酯单体35-50％、腈基单体10-20％、功能单体酸15-25％。
3.根据权利要求1或2任一项所述的方法，其特征在于，所述壳层单体混合液，按照原料的质量比计，包含水20-30％、酰胺类单体10-40％，腈基单体20-50％，功能单体酸15-30％。
4.根据权利要求1-3任一项所述的方法，其特征在于，所述种子预乳化液中单体(包含丙烯酸烷基酯单体、腈基单体、功能单体酸)与壳层单体混合液中单体(包含酰胺类单体、腈基单体、功能单体酸)的质量比为(2-30):(70-95)。
5.根据权利要求1-4任一项所述的方法，其特征在于，所述腈基单体选自丙烯腈和/或甲基丙烯腈。
6.根据权利要求1-5任一项所述的方法，其特征在于，所述功能单体酸选自丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、富马酸和马来酸中的至少一种。
7.根据权利要求1-6任一项所述的方法，其特征在于，所述酰胺类单体选自丙烯酰胺、N-甲基丙烯酰胺、N-乙基丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二乙基丙烯酰胺、2-甲基丙烯酰胺、N-羟甲基丙烯酰胺、N-羟乙基丙烯酰胺、N-羟丙基丙烯酰胺中的至少一种。
8.根据权利要求1-7任一项所述的方法，其特征在于，所述乳化剂选自至少含有一个烯属不饱和官能团的表面活性剂，优选选自烯丙氧基异构醇醚硫酸酯氨盐、烯丙基聚醚磷酸酯、含烯丙基的特种硫醇硫酸盐、烯丙基聚氧化烯醚硫酸酯盐、烯丙基烷基琥珀酸酯磺酸酯盐、烯丙基醚羟基丙磺酸酯盐、聚氧乙烯苯乙烯化苯基醚硫酸酯盐中的至少一种；更优选艾迪科SR-10、上海忠诚精细化工的V-100P。
9.根据权利要求1-8任一项所述的方法制备的溶液型粘剂剂，其特征在于，所述溶液型粘结剂固含量为1-15％，优选3-8％。
10.一种权利要求9所述的方法制得的溶液型粘结剂在锂离子电池负极极片中的应用。
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