CN108221489B - 用于生产无汞锌锰干电池的浆层纸及其制备方法 - Google Patents
用于生产无汞锌锰干电池的浆层纸及其制备方法 Download PDFInfo
- Publication number
- CN108221489B CN108221489B CN201810023240.1A CN201810023240A CN108221489B CN 108221489 B CN108221489 B CN 108221489B CN 201810023240 A CN201810023240 A CN 201810023240A CN 108221489 B CN108221489 B CN 108221489B
- Authority
- CN
- China
- Prior art keywords
- mercury
- coated paper
- dry battery
- free zinc
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- SZKTYYIADWRVSA-UHFFFAOYSA-N zinc manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Zn++] SZKTYYIADWRVSA-UHFFFAOYSA-N 0.000 title claims description 16
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000011247 coating layer Substances 0.000 claims abstract description 37
- 238000005260 corrosion Methods 0.000 claims abstract description 34
- 230000007797 corrosion Effects 0.000 claims abstract description 33
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 239000003112 inhibitor Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 18
- -1 imidazoline quaternary ammonium salt Chemical class 0.000 claims abstract description 11
- 229920000881 Modified starch Polymers 0.000 claims abstract description 10
- 239000004368 Modified starch Substances 0.000 claims abstract description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 10
- 235000019426 modified starch Nutrition 0.000 claims abstract description 10
- 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 claims abstract description 9
- ZCPCLAPUXMZUCD-UHFFFAOYSA-M dihexadecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCC ZCPCLAPUXMZUCD-UHFFFAOYSA-M 0.000 claims abstract description 9
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 9
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 9
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 7
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 7
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 18
- 229920002472 Starch Polymers 0.000 claims description 18
- 229960001484 edetic acid Drugs 0.000 claims description 18
- 239000008107 starch Substances 0.000 claims description 18
- 235000019698 starch Nutrition 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 15
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000006255 coating slurry Substances 0.000 claims description 11
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 11
- 235000018417 cysteine Nutrition 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000006136 alcoholysis reaction Methods 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 7
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 230000005764 inhibitory process Effects 0.000 abstract description 7
- 230000003068 static effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000000123 paper Substances 0.000 description 69
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 27
- 229910052725 zinc Inorganic materials 0.000 description 27
- 239000011701 zinc Substances 0.000 description 27
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 16
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 11
- 229910052753 mercury Inorganic materials 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 208000035404 Autolysis Diseases 0.000 description 2
- 206010057248 Cell death Diseases 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000028043 self proteolysis Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910000645 Hg alloy Inorganic materials 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- YVUZUKYBUMROPQ-UHFFFAOYSA-N mercury zinc Chemical compound [Zn].[Hg] YVUZUKYBUMROPQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/80—Paper comprising more than one coating
- D21H19/84—Paper comprising more than one coating on both sides of the substrate
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
- Primary Cells (AREA)
Abstract
本发明涉及一种用于生产无汞锌锰干电池的浆层纸,其具有基纸和涂覆在基纸两面的涂布层,所述涂布层包括以下质量百分比的组分:变性淀粉60‑69%;聚乙烯醇8‑10%;聚丙烯酰胺6‑7%;氯化双十六烷基二甲基铵4‑5%;羧甲基纤维素钠2‑3%;咪唑啉季铵盐2‑3%;松香聚乙二醇柠檬酸酯1‑2%;复合缓蚀剂8‑10%。本发明还涉及所述用于生产无汞锌锰干电池的浆层纸的制备方法。本发明的用于生产无汞锌锰干电池的浆层纸具有柔软适中、抗静电、缓蚀效果好、涂布层均匀光滑、机械适应性高等优点,能满足高速电池生产线的工艺要求,生产的高容量无汞锌锰干电池性能稳定。
Description
技术领域
本发明涉及干电池制造技术领域,特别是涉及一种用于生产无汞锌锰干电池的浆层纸及其制备方法。
背景技术
锌锰干电池经历了糊式电池和纸板电池两个阶段,至今仍是国内外用量较大的电池之一,由于具有原材料丰富、生产工艺简单、成本低、容量大、适用于大电荷放电、对温度的适应性强、型号多等优点,其用途十分广泛,成为国民经济中不可缺少的一个重要组成部分。
锌锰干电池的电解液呈弱酸性,为氯化锌/氯化铵/水溶液,其正极由二氧化锰、乙炔黑等制成,电池中间插入一根导电流体碳棒,锌具有较低的析氢过电位,用作电池负极兼筒体,正负极之间用一种浆层纸隔离开,确保不会短路,电解液中的导电离子可顺利通过该浆层纸。锌锰干电池的缺点是在使用、储存或间歇放电过程中,作为负极的锌筒与电解液中的酸性物质发生接触而腐蚀造成电池容量下降、溶胀,锌筒变薄导致漏液,从而腐蚀用电设备。由于汞和锌的析氢电位不同,锌汞合金在水环境中析氢过电位较高,因此,长久以来,人们一直采用汞作为缓蚀剂。汞与锌形成的锌汞齐合金,使阳锌表面更均匀,大大提高了阳极锌的析氢过电位,从而减缓了锌电极的自腐蚀速率,显著提高了电池的贮存周期。
然而,汞有剧毒,又极易挥发,废旧电池的汞泄漏入水体和土壤,会在动植物体内富集,最后经过食物链进入到人体。汞金属在人体的某些器官中累积,最终导致汞中毒,为此,2013年10月联合国环境规划署发布了《关于汞的水俣公约》,规定至2020年禁止生产加工汞产品,并限制汞产品的对外贸易。而我国于2016年起已对涉汞企业采取了严格的控制和防范措施。
目前,锌锰干电池厂家大多采用添加铋或贵金属铟来实现电池的无汞化。但由于高容量锌锰电池中天然锰含量大,添加铋作缓蚀剂效果不理想,只有加厚锌筒来弥补其不足,而铟又非常贵,两者都会增大生产成本。同时,电池生产行业为节省用工成本,生产设备自动化程度越来越高,这就需要浆层纸在提供良好的缓蚀效果的同时,还要具备适应于自动化快速生产线所需要达到的柔软性及抗静电性能,以减少生产过程中浆层纸发生破裂、进锌筒困难及掉粉等现象。
因此,需要对浆层纸及其生产工艺进行改革,使浆层纸能够满足高速电池生产线生产高容量无汞锌锰干电池的需求。
发明内容
基于此,本发明的目的在于,提供一种用于生产无汞锌锰干电池的浆层纸,其具有柔软适中、抗静电、缓蚀效果好、涂布层均匀光滑、机械适应性高等优点,能满足高速电池生产线的工艺要求,生产的高容量无汞锌锰干电池性能稳定。
本发明采用的技术方案如下:
一种用于生产无汞锌锰干电池的浆层纸,其具有基纸和涂覆在基纸两面的涂布层,所述涂布层包括以下质量百分比的组分:
其中,变性淀粉在锌锰干电池中充分吸收电解液,发生糊化膨胀,形成电池正负极之间的离子通道,提高离子电导率;聚乙烯醇(PVA)是一种含有许多羧基的亲水化合物,成膜性好,有利于形成均匀光滑的涂布层,且具有保水和糊材粘结的作用;聚丙烯酰胺(PAM)是一种线型高分子聚合物,是很好的保水剂,又作为糊材粘结剂;羧甲基纤维素钠(CMC)是离子型高分子材料,水溶性高,在电池内电阻小,能使浆层纸产生湿强度,减少其润湿变形;氯化双十六烷基二甲基铵,又称双十六烷基二甲基氯化铵,具有良好的化学稳定性、抗静电性和柔软性,与咪唑啉季铵盐表面活性剂配伍,在改善基纸的柔软性的同时,还充当了涂布层的软化剂,且氯化双十六烷基二甲基铵与松香聚乙二醇柠檬酸酯的协同作用,能使产品的抗静电能力增强,从而避免了浆层纸因发硬和静电产生导致在高速电池生产线上出现断纸、破裂引起进锌筒困难等现象,提高了浆层纸的机械适应性;咪唑啉季铵盐表面活性剂还可通过其分子的亲水基改变金属的电化学行为而增大锌电极的自溶阻力,起到一定的缓蚀作用;复合缓蚀剂代替汞,抑制金属锌筒的腐蚀,发挥缓蚀效果。
本发明的配方设计合理,在涂布层中加入了提高纤维和涂层柔软性能的软化剂、除静电剂以及复合缓蚀剂,通过各组分的协同作用,使本发明生产的浆层纸产品柔软适中,抗静电,机械适应性大大提高,适用高速电池生产线的工艺要求,生产的高容量锌锰无汞干电池性能稳定。
进一步地,所述复合缓蚀剂是由质量比例为31:13:25:31的半胱氨酸、氧化铋(Bi2O3)、盐酸(HCl)、乙二胺四乙酸(EDTA)组成。
半胱氨酸能与锌筒表面形成一层致密的络合物半胱氨酸锌盐,该络合物对酸稳定,有效地延缓了锌筒在酸性环境下的腐蚀速度;铋与汞类似,可在锌表面形成合金保护层,从而抑制锌枝晶形成,以提高锌电极的析氢过电位,减少析氢反应发生;EDTA能与锌电极中的金属杂质形成稳定的络合物。通过以上几种物质分子间的优势互补和协同作用,及咪唑啉季铵盐表面活性剂的缓蚀作用,增大了锌的自溶阻力,能较大程度抑制了金属锌筒的腐蚀,尤其对于大比例使用杂质较多的天然锰的高容量电池,缓蚀效果更加明显。
进一步地,所述聚乙烯醇是由醇解度为99-100%的聚乙烯醇(如聚乙烯醇100-27H)与醇解度为86-90%的聚乙烯醇(如聚乙烯醇088-20)按1.25-2:1的质量比例组成。
聚乙烯醇水溶性及其粘度与分子量和醇解度有关,醇解度不同其耐水性和水溶性亦不同,选择上述两种不同醇解度的聚乙烯醇按适宜比例混合使用,能达到更好的成膜效果。
进一步地,所述变性淀粉是由质量比例为6-7:6-7的交联淀粉与交联醚化淀粉组成。
复配交联淀粉与交联醚化淀粉,能够在电解液中达到适宜的糊化程度,提高离子电导率,同时减少浆层纸的电阻,满足高容量电池的生产要求。
进一步地,所述基纸为普通干电池浆层纸用基纸,其一面涂覆的涂布层厚度为30-40μm,另一面涂覆的涂布层厚度为10-20μm。
与现有技术生产的浆层纸相比,本发明浆层纸为双面涂布,且两面涂布层厚度不一,其中贴锌筒一面的厚度为30-40μm,包覆碳粉层一面的厚度为10-20μm,在总厚度不变的情况下,增加贴锌筒一面的涂布层厚度能提高电池贮存期,而减少包覆碳粉层一面的涂布层厚度能降低电池内阻,从而提高电性能。
本发明的另一目的在于,提供上述的用于生产无汞锌锰干电池的浆层纸的制备方法,该制备方法包括以下步骤:
(1)制备胶体:按配比将聚乙烯醇和聚丙烯酰胺加入去离子水中,加热搅拌制成胶体;
(2)制备淀粉溶液:将变性淀粉与去离子水配制成淀粉溶液;
(3)制备复合缓蚀剂溶液:先将氧化铋溶于浓盐酸中,得到氧化铋溶液,将乙二胺四乙酸溶于去离子水中,得到乙二胺四乙酸溶液,然后将氧化铋溶液缓慢加入乙二胺四乙酸溶液中并搅拌,最后加入半胱氨酸,混合均匀后得到复合缓蚀剂溶液;
(4)制备涂布浆料:按配比将制备好的胶体、淀粉溶液、复合缓蚀剂溶液、氯化双十六烷基二甲基铵、羧甲基纤维素钠、咪唑啉季铵盐与松香聚乙二醇柠檬酸酯混合均匀,得到涂布浆料;
(5)涂布与干燥:将制备好的涂布浆料均匀涂覆在基纸两面,干燥后得到所述的用于生产无汞锌锰干电池的浆层纸。
进一步地,步骤(1)中,聚乙烯醇和聚丙烯酰的总质量与去离子水的质量比例为1:30,加热温度为100℃,加热搅拌时间为30分钟。
进一步地,步骤(2)中,变性淀粉与去离子水的质量比例为1:1。
进一步地,步骤(3)制得的复合缓蚀剂溶液中,半胱氨酸、氧化铋(Bi2O3)、盐酸(HCl)、乙二胺四乙酸(EDTA)的质量比例为31:13:25:31,半胱氨酸、氧化铋、盐酸、乙二胺四乙酸的总质量与去离子水的质量比例为1:10。
进一步地,步骤(4)具体为:先将冷却后的胶体溶液加入搅拌锅中,在搅拌过程中先缓慢加入复合缓蚀剂溶液,搅拌20分钟后加入淀粉溶液,再搅拌20分钟后加入氯化双十六烷基二甲基铵、羧甲基纤维素钠、咪唑啉季铵盐和松香聚乙二醇柠檬酸酯,搅拌混合均匀后得到涂布浆料。
为了更好地理解和实施,下面结合附图详细说明本发明。
附图说明
图1为本发明的用于生产无汞锌锰干电池的浆层纸的结构示意图;
图2为浆层纸制备中步骤(1)至(4)的工艺流程图;
图3为浆层纸制备中步骤(5)的工艺流程图。
具体实施方式
请参阅图1,其为本发明的用于生产无汞锌锰干电池的浆层纸的结构示意图。
所述用于生产无汞锌锰干电池的浆层纸具有基纸10以及分别涂覆在基纸10两面的涂布层21和涂布层22。
所述基纸10为普通干电池浆层纸用基纸。所述涂布层21的厚度为30-40μm,所述涂布层22的厚度为10-20μm。
所述浆层纸用于生产无汞锌锰干电池时,基纸10中涂覆涂布层21的一面贴于锌筒的筒面,涂覆涂布层22的一面用于包覆碳粉层。
所述涂布层21和涂布层22的材料配方相同,包括以下质量百分比的组分:
具体地,所述变性淀粉是由质量比例为6-7:6-7的交联淀粉与交联醚化淀粉组成。
所述聚乙烯醇是由聚乙烯醇100-27H与聚乙烯醇088-20按1.25-2:1的质量比例组成。
所述复合缓蚀剂是由质量比例为31:13:25:31的半胱氨酸、氧化铋、盐酸、EDTA组成。
请参阅图2和图3,图2为浆层纸制备中步骤(1)至(4)的工艺流程图,图3为浆层纸制备中步骤(5)的工艺流程图。所述用于生产无汞锌锰干电池的浆层纸的制备方法具体按如下步骤进行:
(1)制备胶体:按配比将聚乙烯醇和聚丙烯酰胺加入去离子水中,其中聚乙烯醇和聚丙烯酰的总质量与去离子水的质量比例为1:30,然后加热至100℃,并在保温下搅拌30分钟,制成胶体。
(2)制备淀粉溶液:按质量比例为1:1将变性淀粉加入去离子水中,搅拌,使其充分浸润,配制成淀粉溶液。
(3)制备复合缓蚀剂溶液:先将氧化铋溶于浓盐酸中,得到氧化铋溶液,将EDTA溶于去离子水中,得到EDTA溶液,然后按配比将氧化铋溶液缓慢加入EDTA溶液中并搅拌,最后按配比加入半胱氨酸,混合均匀后得到复合缓蚀剂溶液。制得的复合缓蚀剂溶液中,半胱氨酸、氧化铋、盐酸、EDTA的总质量与去离子水的质量比例为1:10。
(4)制备涂布浆料:先将冷却后的胶体溶液加入搅拌锅中,在搅拌过程中先缓慢加入复合缓蚀剂溶液,搅拌20分钟后加入淀粉溶液,再搅拌20分钟后分别加入氯化双十六烷基二甲基铵、咪唑啉季铵盐和松香聚乙二醇柠檬酸酯,羧甲基纤维素钠用适量去离子水溶解后一并加入,搅拌混合均匀后得到涂布浆料。
(5)涂布与干燥:将制备好的涂布浆料分别均匀涂覆在普通干电池浆层纸用基纸的两面,烘干后得到所述的用于生产无汞锌锰干电池的浆层纸,再将其收卷好备用。
实施例一
本实施例提供的浆层纸中涂布层的材料配方如下(按质量百分比计):
上述配方制得的浆层纸柔软性好,干、湿强度好,其涂布层与基纸粘接牢固,且涂布层均匀光滑;用于生产锌锰干电池时,该浆层纸进筒顺利,无破裂、无掉粉、无静电现象产生,完全能够满足高速电池生产线的生产工艺要求,生产所得的高容量锌-锰干电池能达到工艺要求的电性能。
实施例二
本实施例提供的浆层纸中涂布层的材料配方如下(按质量百分比计):
上述配方制得的浆层纸柔软性好,干、湿强度好,其涂布层与基纸粘接牢固,且涂布层均匀光滑;用于生产锌锰干电池时,该浆层纸进筒顺利,无破裂、无掉粉、无静电现象产生,完全能够满足高速电池生产线的生产工艺要求,生产所得的高容量锌-锰干电池能达到工艺要求的电性能。
实施例三
本实施例提供的浆层纸中涂布层的材料配方如下(按质量百分比计):
上述配方制得的浆层纸柔软性好,干、湿强度好,其涂布层与基纸粘接牢固,且涂布层均匀光滑;用于生产锌锰干电池时,该浆层纸进筒顺利,无破裂、无掉粉、无静电现象产生,完全能够满足高速电池生产线的生产工艺要求,生产所得的高容量锌-锰干电池能达到工艺要求的电性能。
生产实践证明,本发明的用于生产无汞锌锰干电池的浆层纸,在生产大比例天然锰的高容量电池时缓蚀效果显著,涂布层与基纸粘接牢固,且均匀光滑,该浆层纸质地柔软,干、湿强度好。生产锌锰干电池时,所述浆层纸进筒顺利,无破裂、无掉粉、无静电现象产生,完全能满足高速电池生产线的生产工艺要求,生产的高容量无汞锌锰干电池能达到工艺要求的电性能,经济效益明显。本发明的浆层纸用于生产大比例天然锰R6高容量电池时,使用2.9g锌筒即能达到工艺要求,而现有工艺生产的浆层纸需使用3.2g锌筒才能达到工艺要求。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。
Claims (9)
1.一种用于生产无汞锌锰干电池的浆层纸,其特征在于:具有基纸和涂覆在基纸两面的涂布层,所述涂布层包括以下质量百分比的组分:
所述复合缓蚀剂是由质量比例为31:13:25:31的半胱氨酸、氧化铋、盐酸、乙二胺四乙酸组成。
2.根据权利要求1所述的用于生产无汞锌锰干电池的浆层纸,其特征在于:所述聚乙烯醇是由醇解度为99-100%的聚乙烯醇与醇解度为86-90%的聚乙烯醇按1.25-2:1的质量比例组成。
3.根据权利要求1所述的用于生产无汞锌锰干电池的浆层纸,其特征在于:所述变性淀粉是由质量比例为6-7:6-7的交联淀粉与交联醚化淀粉组成。
4.根据权利要求1-3任一项所述的用于生产无汞锌锰干电池的浆层纸,其特征在于:所述基纸为普通干电池浆层纸用基纸,其一面涂覆的涂布层厚度为30-40μm,另一面涂覆的涂布层厚度为10-20μm。
5.权利要求1-4任一项所述的用于生产无汞锌锰干电池的浆层纸的制备方法,其特征在于:包括以下步骤:
(1)制备胶体:按配比将聚乙烯醇和聚丙烯酰胺加入去离子水中,加热搅拌制成胶体;
(2)制备淀粉溶液:将变性淀粉与去离子水配制成淀粉溶液;
(3)制备复合缓蚀剂溶液:先将氧化铋溶于浓盐酸中,得到氧化铋溶液,将乙二胺四乙酸溶于去离子水中,得到乙二胺四乙酸溶液,然后将氧化铋溶液缓慢加入乙二胺四乙酸溶液中并搅拌,最后加入半胱氨酸,混合均匀后得到复合缓蚀剂溶液;
(4)制备涂布浆料:按配比将制备好的胶体、淀粉溶液、复合缓蚀剂溶液、氯化双十六烷基二甲基铵、羧甲基纤维素钠、咪唑啉季铵盐与松香聚乙二醇柠檬酸酯混合均匀,得到涂布浆料;
(5)涂布与干燥:将制备好的涂布浆料均匀涂覆在基纸两面,干燥后得到所述的用于生产无汞锌锰干电池的浆层纸。
6.根据权利要求5所述的用于生产无汞锌锰干电池的浆层纸的制备方法,其特征在于:步骤(1)中,聚乙烯醇和聚丙烯酰的总质量与去离子水的质量比例为1:30,加热温度为100℃,加热搅拌时间为30分钟。
7.根据权利要求5所述的用于生产无汞锌锰干电池的浆层纸的制备方法,其特征在于:步骤(2)中,变性淀粉与去离子水的质量比例为1:1。
8.根据权利要求5所述的用于生产无汞锌锰干电池的浆层纸的制备方法,其特征在于:步骤(3)制得的复合缓蚀剂溶液中,半胱氨酸、氧化铋、盐酸、乙二胺四乙酸的质量比例为31:13:25:31,半胱氨酸、氧化铋、盐酸、乙二胺四乙酸的总质量与去离子水的质量比例为1:10。
9.根据权利要求5所述的用于生产无汞锌锰干电池的浆层纸的制备方法,其特征在于:步骤(4)具体为:先将冷却后的胶体溶液加入搅拌锅中,在搅拌过程中先缓慢加入复合缓蚀剂溶液,搅拌20分钟后加入淀粉溶液,再搅拌20分钟后加入氯化双十六烷基二甲基铵、羧甲基纤维素钠、咪唑啉季铵盐和松香聚乙二醇柠檬酸酯,搅拌混合均匀后得到涂布浆料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810023240.1A CN108221489B (zh) | 2018-01-10 | 2018-01-10 | 用于生产无汞锌锰干电池的浆层纸及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810023240.1A CN108221489B (zh) | 2018-01-10 | 2018-01-10 | 用于生产无汞锌锰干电池的浆层纸及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108221489A CN108221489A (zh) | 2018-06-29 |
CN108221489B true CN108221489B (zh) | 2019-01-29 |
Family
ID=62641724
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810023240.1A Active CN108221489B (zh) | 2018-01-10 | 2018-01-10 | 用于生产无汞锌锰干电池的浆层纸及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108221489B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109616677B (zh) * | 2018-12-10 | 2020-11-10 | 杭州长命电池有限公司 | 一种糊式无汞电池浆液及其制备方法 |
CN111304959B (zh) * | 2020-02-26 | 2021-11-19 | 常州大学 | 一种防漏型无汞电池用浆层纸的制备方法 |
CN113201971A (zh) * | 2021-05-06 | 2021-08-03 | 连州市凌力电池配件有限公司 | 一种增加碳性电池耐漏液性能的浆层纸及其制备方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100454628C (zh) * | 2005-03-29 | 2009-01-21 | 嘉善宇河特种纸品有限公司 | 无汞锌锰电池浆层纸 |
CN101392477A (zh) * | 2008-10-22 | 2009-03-25 | 广东肇庆明珠纸业有限公司 | 代汞缓蚀剂锌-锰干电池浆层纸 |
CN101798778B (zh) * | 2010-03-09 | 2011-06-15 | 肖勇 | 用于高速电池生产线的无汞锌-锰干电池浆层纸及其制备方法 |
CN103147348B (zh) * | 2013-03-28 | 2015-11-18 | 肖勇 | 用k8电缆纸生产的高速电池生产线用浆层纸及制备方法 |
CN103789773B (zh) * | 2014-01-16 | 2016-05-04 | 河北科技大学 | 一种浆层纸用有机复合缓蚀剂及其浆料 |
-
2018
- 2018-01-10 CN CN201810023240.1A patent/CN108221489B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN108221489A (zh) | 2018-06-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108221489B (zh) | 用于生产无汞锌锰干电池的浆层纸及其制备方法 | |
CN100428546C (zh) | 碱性电池 | |
CN110993884B (zh) | 锂离子电池负极浆料、制备方法、负极极片以及电池 | |
CA2126071A1 (en) | Low mercury or mercury free alkaline manganese dioxide-zinc cell | |
CN109119632A (zh) | 正极浆料、正极片及锂离子电池 | |
CN110783560B (zh) | 一种含有改性纳米锌粉的碱性锌锰电池及其制备方法 | |
CN103789773A (zh) | 一种浆层纸用有机复合缓蚀剂及其浆料 | |
CN113571839A (zh) | 适用于二次锌基电池的功能化复合隔膜及制备方法与应用 | |
CN105514505A (zh) | 一种深循环阀控铅酸电池及其制备方法 | |
CN101271968A (zh) | 叠层电池所用的无汞隔膜纸 | |
CN106252654B (zh) | 抑制氧化的铅酸蓄电池负极铅膏 | |
CN201478380U (zh) | 一种镍氢电池极片及使用该种极片的电池 | |
CN109742331A (zh) | 一种二次镍氢电池的负极片及其制作方法 | |
CN111304959B (zh) | 一种防漏型无汞电池用浆层纸的制备方法 | |
CN113839003B (zh) | 一种镍锌电池负极片的制备方法 | |
CN109167051A (zh) | 一种高镍体系的三元材料及高容量电池 | |
CN113054262B (zh) | 一种用于锌镍电池的水凝胶电解质、锌镍电池及制备方法 | |
JP2011210640A (ja) | 鉛蓄電池用正極活物質及びそれを充填して成る鉛蓄電池用正極板 | |
US3713891A (en) | Chloride free leaching process for porous zinc anodes | |
CN1039067C (zh) | 无汞锌锰纸板电池 | |
CN101702430A (zh) | 一种碱性锌电池复合添加剂及其制备方法与应用 | |
JP2012209048A (ja) | 印刷電池 | |
Zhang et al. | Further studies of a zinc-air cell employing a Zn-PCH (PVA chemical hydrogel) anode | |
KR100588089B1 (ko) | 초박형 망간전지의 양극 및 그의 제조방법 | |
CN110729527A (zh) | 一种用于锌空电池的高稳定性电解质及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20210624 Address after: 136600 No.27 Jinfu Road, Weijin Town, Dongliao County, Liaoyuan City, Jilin Province Patentee after: Liaoyuan Jinyu Chengcheng diaphragm Co.,Ltd. Address before: 526600 east side plot of Kangjie Road, industrial intensive base, Deqing County, Zhaoqing City, Guangdong Province Patentee before: GUANGDONG ZHAOQING MINGZHU PAPER Co.,Ltd. |