CN113113598B - 水系锌基镍钴电池正极材料及其制备方法 - Google Patents
水系锌基镍钴电池正极材料及其制备方法 Download PDFInfo
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 20
- 239000011701 zinc Substances 0.000 title claims abstract description 20
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- 239000006260 foam Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims description 15
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims description 14
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 18
- HIDACJPWCRPEDW-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Ni+2].[Co+2] Chemical compound P(=O)([O-])([O-])[O-].[Ni+2].[Co+2] HIDACJPWCRPEDW-UHFFFAOYSA-K 0.000 abstract description 15
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 239000010405 anode material Substances 0.000 abstract description 8
- 239000002135 nanosheet Substances 0.000 abstract description 7
- 150000003751 zinc Chemical class 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910002441 CoNi Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910018487 Ni—Cr Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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Abstract
本发明公开了一种水系锌基镍钴正极材料。所述的正极材料是在三维基底上长出的纳米片状镍钴磷酸盐,所述的负极为锌片,所述电解液为一定浓度的氢氧化钾和可溶性锌盐水溶液。与现有的技术相比,本发明首次将过渡金属磷酸盐复合材料应用于水系锌基镍钴电池体系,通过泡沫镍上原位制备的镍钴磷酸盐拥有高比表面积的纳米片状结构,具有高比容量和良好的循环稳定性,且制备工艺简单,适合用于大规模生产。
Description
技术领域
本发明属于高能水系电池技术领域,具体涉及到一种高能水系锌基镍钴电池正极材料。
背景技术
随着人类社会的进步和电子设备的普及,以及低碳环保的电动交通的大力推广,人类对于二次电池的需求越来越大。二次电池是一种高效储能装置,可以实现重复充放电和循环使用,与一次电池相比二次电池具有污染小成本低等特点。目前主要的二次电池技术包括镍铬电池、镍氢电池、铅酸电池和锂离子电池等等。镍铬电池和铅酸电池出现的较早,但都存在容量较低和使用寿命较短的缺点,并且电池里的重金属对环境会造成巨大的污染,所用发展前景有限。锂离子电池是目前应用最为广泛的一类电池,但与此同时对锂的需求量快速增长,而全球锂的储量有限,导致价格迅速上涨,不符合低成本需求,且锂离子电池使用的有机电解液易燃,存在很大的安全问题。
而水系锌基镍钴电池则是近年来兴起的二次电池,相比于镍铬电池和铅酸电池,它具有更高的电池容量和更长的使用寿命,且没有重金属不会对环境造成很大的危害。与锂离子电池相比,锌的储量比锂要丰富,成本上会比锂离子电池低很多,而且电解质是氢氧化钾的水溶液,不会引起燃烧和爆炸,安全性相对较高,在大型储能领域具备很高的潜在价值。通过水热法制备的磷酸钴纳米片具有很大的比表面积,增强了离子可及性并且缩短了离子扩算途径,加快了电子传导,导致了更高的比容量,并且减少面容量损失,导致更长的循环稳定性。镍和钴在元素周期表中都是第四周期元素,并且位置相邻,具有相似的原子结构,可以大胆猜想镍钴掺杂的正极材料也可以达到同样甚至更好的效果。
发明内容
本发明的目的是提供一种水系锌基镍钴电池。该电池组成包括电池正极材料,负极材料和电解质溶液。电池的正极材料是一种在三维基底上均匀生长的纳米片状镍钴磷酸盐复合材料,它具有原材料丰富、稳定性好和比容量高等特点。该方法反应条件温和,成本低廉,可运用于大规模生产。电池的负极材料是锌片,电解液是一定浓度的氢氧化钾和可溶性锌盐水溶液,可以有效的防止电池的腐蚀和钝化问题。
本发明所述的水系锌基镍钴电池包括电池正极材料、负极材料和电解液,所述的正极材料为三维基底上长出的纳米片状镍钴磷酸盐,所述的负极材料为锌片,所述的电解质包括一定浓度的氢氧化钾和可溶性锌盐水溶液。
本发明所述的正极材料为镍钴磷酸盐材料,该材料为NixCo3-x(PO4)2,其中0≤x≤3。
水系锌基镍钴电池正极材料的制备方法包括如下步骤:
室温条件下将钴(镍)盐、磷酸盐混合后溶于去离子水中,所得溶液转入放有三维基底材料的水热釜中进行水热反应,待冷却后,将泡沫镍取出冲洗、烘干,得到生长在三维基底的磷酸钴镍材料。
本发明所述正极材料制备时使用的钴盐、镍盐和磷酸盐浓度为0.0001~0.5mol/L。
本发明所述正极材料制备时使用的钴盐包括硝酸钴、氯化钴、硫酸钴或醋酸钴。镍盐包括硝酸镍、氯化镍、硫酸镍或醋酸镍。
本发明所述正极材料制备时使用的磷酸盐包括磷酸二氢铵、磷酸二氢钾或磷酸二氢钠。
本发明所述正极材料制备时使用的钴盐和镍盐关系为任意比。
本发明所述正极材料制备时溶液体积为高压反应釜体积的50%~90%。
本发明所述的水热反应温度条件为:100℃~200℃下反应1~36h。
本发明所述的正极材料制备时在50~80℃下干燥1~12h,得到水系锌基镍钴电池正极材料。
本发明所述的正极材料制备时所用的三维基底包括碳纸、泡沫镍、钛合金网或不锈钢网中的任意一种。
本发明所述的负极材料为锌片、锌箔或锌粉。
本发明所述的电解液包括一定浓度的氢氧化钾和可溶性锌盐。
本发明所述的电解液中氢氧化钾的浓度为0.1-10M。
本发明所述的电解液中锌盐的种类包括氯化锌、硫酸锌、硝酸锌、或醋酸锌。
本发明与现有技术相比,具有如下优点:
本发明的水系锌基镍钴电池由电池正极,负极和电解液组成。本发明首次将镍钴磷酸盐应用于锌基镍钴电池的研究,正极是通过一步水热法合成了在三维基底上均匀生长的纳米片负载纳米片状镍钴磷酸盐复合材料,拥有较大的比表面积。该材料原材料丰富、稳定性好、比容量高,从而表现出优越的电化学性能。本发明公开的镍钴磷酸盐材料具有极高的容量,在一定扫速下还原峰峰值可达100mA/cm2以上,并且随着浓度提高还原峰峰值还有不断的显著提升。经过调整镍钴的组成探究出了一个最佳组成比例,该材料的还原峰峰值可达350mA/cm2以上,这些峰值转换的容量比起同一领域其他工艺制备的材料的容量要高得多。
附图说明
图1为实施例1中反应物是(a)Co3(PO4)2-1(b)Co3(PO4)2-2条件下生长在泡沫镍基底上的磷酸钴的SEM图。
图2为实施例1中反应物是(a)Co3(PO4)2-1(b)Co3(PO4)2-2条件下生长在泡沫镍基底上的磷酸钴的CV图。
图3为实施例2中反应物是Ni3(PO4)2、CoNi2(PO4)2、Co1.5Ni1.5(PO4)2、Co2Ni(PO4)2和Co3(PO4)2-2条件下生长在泡沫镍基底上的磷酸镍钴的CV图。
图4为实施例2中反应物是Ni3(PO4)2、CoNi2(PO4)2、Co1.5Ni1.5(PO4)2、Co2Ni(PO4)2和Co3(PO4)2-2条件下生长在泡沫镍基底上的磷酸镍钴的GCD图。
图5为实施例2中Co1.5Ni1.5(PO4)2组成的锌基镍钴电池的稳定性图。
具体实施方式
以下结合实施例旨在进一步说明本发明,而非限制本发明。
实施例1
将四份浓度为1.2mM的磷酸二氢铵和1.8mM的硝酸钴溶入80ml的去离子水中,并分别加入0.01M和0.05M的尿素,在室温条件下搅拌得到粉红色溶液,所得溶液转入放有泡沫镍(2*4cm2)的水热釜中进行水热反应,水热反应的温度为120℃,保温时间为6h,待冷却后,将泡沫镍取出多次冲洗,然后放入60℃烘箱中干燥。得到生长在泡沫镍基底的磷酸钴材料(分别标记为Co3(PO4)2-1和Co3(PO4)2-2)。
图1(a)为本发明实施例1制备得到的磷酸钴样品Co3(PO4)2-1的SEM图。如图可以看出,通过一步水热法成功的在泡沫镍基底上生长出了纳米片状磷酸钴,并且这些纳米片状结构能够在泡沫镍上均匀紧凑的排布。图1(b)是磷酸钴样品Co3(PO4)2-2的SEM图,可以看出和图1(a)的形貌仍然保留,并在之前的纳米片状结构上又负载了一层致密的纳米颗粒。
图2为实施例1中磷酸钴样品Co3(PO4)2-1和Co3(PO4)2-2的循环伏安曲线,可以看出磷酸钴样品Co3(PO4)2-2的氧化还原峰相比于原样品来说增加到了160mA/cm2。反映出尿素添加的含量调控对样品性能的优化。
实施例2
将浓度为1.2mM的磷酸二氢铵、1.8mM的硝酸镍和0.05M的尿素溶入80ml的去离子水中,在室温条件下搅拌得到粉红色溶液,所得溶液转入放有泡沫镍(2*4cm2)的水热釜中进行水热反应,水热反应的温度为120℃,保温时间为6h,待冷却后,将泡沫镍取出多次冲洗,然后放入60℃烘箱中干燥。得到生长在泡沫镍基底的磷酸钴材料(标记为Ni3(PO4)2)。
方法同上述补正,仅硝酸钴调整为0.6mM硝酸钴和1.2mM硝酸镍,得到的产品为生长在泡沫镍基底的磷酸镍钴材料(标记为CoNi2(PO4)2)。
方法同上述补正,仅硝酸钴调整为0.9mM硝酸钴和0.9mM硝酸镍,得到的产品为生长在泡沫镍基底的磷酸镍钴材料(标记为Co1.5Ni1.5(PO4)2)。
方法同上述补正,仅硝酸钴调整为1.2mM硝酸钴和0.6mM硝酸镍,得到的产品为生长在泡沫镍基底的磷酸镍钴材料(标记为Co2Ni(PO4)2)。
图3为实施例2中磷酸钴样品Ni3(PO4)2、CoNi2(PO4)2、Co1.5Ni1.5(PO4)2、Co2Ni(PO4)2和实施例1中Co3(PO4)2-2的循环伏安曲线,可以明显看出不同镍钴的比例对样品性能的影响很大,其中镍钴比为1:1时样品的性能最好,还原峰的电流密度能够达到380 mA/cm2。
图4为实施例2中磷酸钴样品Ni3(PO4)2、CoNi2(PO4)2、Co1.5Ni1.5(PO4)2和Co2Ni(PO4)2在5mA/cm2电流密度下的充放电曲线,可以看到反应出的性能规律与图3相符合,仍然是Co1.5Ni1.5(PO4)2的性能最好,一次恒流充放电所用时长可达5000s以上。
图5为实施例2中磷酸镍钴样品Co1.5Ni1.5(PO4)2组成的锌钴电池在50mA/cm2的恒定电流下的稳定性测试图,可以看出磷酸钴样品Co1.5Ni1.5(PO4)2在3000次充放电的过程中库伦效率一直接近百分之百,说明反应过程的转化效率极高,并且经过3000次循环后的容量仍然能够保持在初始容量的65%以上,由此可见该材料具有很好的循环稳定性。
Claims (1)
1.一种水系锌基镍钴电池正极材料的制备方法,其特征在于,水系锌基镍钴电池正极材料的制备方法包括如下步骤:
将浓度为1.2mM的磷酸二氢铵、0.9mM硝酸钴和0.9mM硝酸镍和0.05M的尿素溶入80ml的去离子水中,在室温条件下搅拌得到粉红色溶液,所得溶液转入放有泡沫镍2*4cm2的水热釜中进行水热反应,水热反应的温度为120℃,保温时间为6h,待冷却后,将泡沫镍取出多次冲洗,然后放入60℃烘箱中干燥,得到生长在泡沫镍基底的磷酸钴材料Co1.5Ni1.5(PO4)2。
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