CN106654260A - 一种锂电池磷酸钒锂电极活性材料的生产制备工艺方法 - Google Patents
一种锂电池磷酸钒锂电极活性材料的生产制备工艺方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 8
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 title abstract description 3
- 239000011149 active material Substances 0.000 title abstract description 3
- 239000007921 spray Substances 0.000 claims abstract description 22
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 13
- 229910052720 vanadium Inorganic materials 0.000 claims description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007772 electrode material Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000012047 saturated solution Substances 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000011555 saturated liquid Substances 0.000 abstract 2
- 238000005507 spraying Methods 0.000 abstract 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 5
- 229910052493 LiFePO4 Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- -1 Polytetrafluoroethylene Polymers 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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
- H01M4/36—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种锂电池磷酸钒锂电极活性材料的生产制备工艺方法,包括以下步骤:首先制备非化学计量比的Li3‑3xV2+x(PO4)3的炮和溶液,然后在恒压恒速的条件下,将步骤S1得到的饱和溶液送入喷雾干燥器中经过雾化喷出,与此同时从喷雾干燥塔的切向方向送入干燥的热风,所述热风气流方向与溶液喷出的方向同向,所述喷雾干燥器的顶部还设有抽真空设备将喷雾干燥器内的湿风引出,并在底部得到干燥的超细颗粒的原料粉末。本发明更加适合大规模工业化生产,且相对于磷酸铁锂的生产工艺方法,更简单、效率更高,产品质量可控。
Description
技术领域
本发明主要涉及锂电池活性材料磷酸钒锂的生产制备工艺方法。
背景技术
锂离子二次动力电池的发展是新能源汽车发展的关键所在,而动力电池的充电时间是制约电动汽车发展的主要瓶颈之一。磷酸盐系正极材料是一类很有特色的正极材料,与传统的钴酸锂、锰酸锂以及三元材料相比,材料结构更为稳定。稳定的结构带来了良好的安全性能,优良的库伦效率和较长的循环寿命,非常适合作为高能动力电池的新型正极材料。与磷酸铁锂不同,本项目选择的磷酸钒锂(Li3V2(PO4)3)正极材料不仅具有良好的安全性,并且具有更高的Li+离子扩散系数,更高的放电电压(4.1V)和能量密度(2330mWh/cm3),兼具了钴酸锂和磷酸铁锂的优点,克服了上述两者的缺点。发明人前期的工作(在先申请号:201410398894.4)通过制备非化学计量比Li3-3xV2+x(PO4)3:将锂源、钒源、磷源和碳源按照摩尔比为(3-3x:2+x:3:2)(分别以锂元素、钒元素、磷元素和碳源计),当x=0.10,Li3- 3xV2+x(PO4)3作为锂离子动力电池正极材料表现出优异的电化学性能。
然而具有优良充放电性能的非整理磷酸钒锂作为正极材料,应用于锂离子电池,还需要能够批量生产的工业化生产线。而前面专利申请所提及的制备工艺是在实验室条件下完成,并不适合直接用于大规模工业化生产。
磷酸钒锂与磷酸铁锂类似,都需要在隔绝氧气的环境下制备,因此工艺上可以借鉴磷酸铁锂的制备工艺,通常可以采用混料,粗磨,细磨(砂磨),喷雾干燥,高温烧结,粉碎,包装等工艺。这样的工艺步骤繁多,如果能简化工艺,将极大的节省生产的成本,加快产品的生产速度,提高产量,并且增加产品质量的可控性。
发明内容
发明目的:针对上述现有存在的问题和不足,本发明的目的是提供了一种锂电池磷酸钒锂电极活性材料的生产制备工艺方法,更加适合大规模工业化生产,且相对于磷酸铁锂的生产工艺方法,更简单、效率更高,产品质量可控。
技术方案:为实现上述发明目的,本发明采用以下技术方案:一种锂电池磷酸钒锂电极活性材料的生产制备工艺方法,包括以下步骤:
S1:非化学计量比的Li3-3xV2+x(PO4)3溶液制备:将锂源、钒源、磷源和碳源按照摩尔比为(3-3x):(2+x):3:y的比例溶于水,并搅拌均匀制成均一的饱和溶液,其中0<x<0.15,1.5≤y<3;
S2:然后在恒压恒速的条件下,将步骤S1得到的饱和溶液送入喷雾干燥器中经过雾化喷出,与此同时从喷雾干燥塔的切向方向送入干燥的热风,所述热风气流方向与溶液喷出的方向同向,所述喷雾干燥器的顶部还设有抽真空设备将喷雾干燥器内的湿风引出;
S3:喷雾干燥器底部收集得到干燥的超细颗粒的原料粉末;
S4:所述原料粉末在惰性气体的保护下高温烧结1~10h,烧结温度为600~850℃;
S5:最后冷却并粉碎,产品包装。
作为优选,步骤S1中碳源为柠檬酸、蔗糖、葡萄糖、聚乙二醇、抗坏血酸或草酸氢铵。
作为优选,步骤S1中碳源为抗坏血酸或草酸氢铵。
进一步改进,步骤S1中,首先将钒源溶于水得到五价钒溶液,然后继续加入碳源进行预反应得到三价钒溶液的前驱体,继续加入剩余计量的锂源和磷源,搅拌溶解;此过程中碳源加入的量的相对值范围为1.5≤y<1.8。
作为优选,所述钒源为偏钒酸铵。
作为优选,所述锂源为碳酸锂、氢氧化锂、醋酸锂或硝酸锂中的一种或多种的混合物。
作为优选,所述磷源为磷酸二氢铵、磷酸氢二铵、磷酸铵或磷酸中的一种或多种的混合物。
有益效果:本发明采用喷雾干燥法直接对雾化的原料饱和溶液进行气液相接触热交换,能迅速干燥得到磷酸钒锂超细颗粒,符合大规模工业化生产;通过预处理降低碳源的使用量和优选粘度小的碳源从而减少过剩碳源,进而避免原料饱和溶液粘连在喷雾干燥器的内壁,能迅速干燥。
具体实施方式
下面结合具体实施例,进一步阐明本发明,应理解这些实施例仅用于说明本发明而不用于限制本发明的范围,在阅读了本发明之后,本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定的范围。
发明人的在先专利(申请号:201410398894.4)公开的磷酸钒锂的制备方法适合在实验室制备,做放大试验后遇到以下技术问题:(1)现有的磷酸钒锂的制备方法都是配制成溶液,然后在浴锅中加热不断浓缩成凝胶,再进行真空干燥,最后研磨烧结,该生产过程程序复杂,且能耗高效率低,显然不适合大规模生产。(2)由于原料采用工业级(实验室采用的分析纯)且一次生产批量大,配制的原料饱和溶液在经过喷雾干燥时,极易出现粘稠液滴粘附,影响生产效率。
本发明采用喷雾造粒的方法进行干燥制备磷酸钒锂的干燥超细颗粒,但在按照原物料配比时雾化液滴极易团聚粘附在喷雾干燥器的内壁甚至滴落到生产地面,极大影响了干燥效率并污染操作环境。因此发明人进一步改进,具体生产方法如下:
首先将偏钒酸铵溶于水得到五价的偏钒酸铵溶液,然后继续加入碳源进行预还原反应得到三价钒溶液的前驱体,此时可以尽可能避免一次物料混合可能造成的碳源过量。然后继续加入剩余计量的醋酸锂和磷酸二氢铵,搅拌溶解得到饱和溶液,其中:锂源、钒源、磷源和碳源按照摩尔比为(3-3x):(2+x):3:y,x取值0.08,y取值只需1.6即可,从而可以降低碳源的添加量。
然后在恒压恒速的条件下,将得到的饱和溶液送入喷雾干燥器中经过雾化喷出,与此同时从喷雾干燥塔的切向方向送入干燥的热风,所述热风气流方向与溶液喷出的方向同向,所述喷雾干燥器的顶部还设有抽真空设备将喷雾干燥器内的湿风引出。此过程中,干燥的热风气流与雾化液滴接触发生迅速的传质传热,并在真空设备的抽离下排出,最后留下干燥的磷酸钒锂超细颗粒。在工业化放大生产过程中,碳源(尤其是柠檬酸和蔗糖)的使用量较大容易在喷雾干燥过程中形成粘稠的液滴粘附在干燥器内壁或滴落在地面,极大影响干燥效率和干燥效果。本发明人一方面通过减少碳源的使用量,另一方面优选使用抗坏血酸或草酸氢铵等粘稠较低的碳源还原剂,同时还利用抽真空旋风分离方式及时抽离吸湿后气流,从而快速得到干燥的磷酸钒锂。
电极即将上述制得的磷酸钒锂样品与乙炔黑、碳管、聚偏氟乙烯(简称PVDF)或者聚四氟乙烯(简称PTFE)按照一定的比例混合,研磨均匀糊与N-甲基甲基吡咯烷酮(NMP)混合后经过搅拌器搅拌均匀后得到混合悬浊液,均匀涂布在铝箔上,经过真空干燥箱烘干后切片即得到电极片。制备流程包括制浆-涂装-制片。
Claims (7)
1.一种锂电池磷酸钒锂电极活性材料的生产制备工艺方法,其特征在于包括以下步骤:
S1:非化学计量比的Li3-3xV2+x(PO4)3溶液制备:将锂源、钒源、磷源和碳源按照摩尔比为(3-3x):(2+x):3:y的比例溶于水,并搅拌均匀制成均一的饱和溶液,其中0<x<0.15,1.5≤y<3;
S2:然后在恒压恒速的条件下,将步骤S1得到的饱和溶液送入喷雾干燥器中经过雾化喷出,与此同时从喷雾干燥塔的切向方向送入干燥的热风,所述热风气流方向与溶液喷出的方向同向,所述喷雾干燥器的顶部还设有抽真空设备将喷雾干燥器内的湿风引出;
S3:喷雾干燥器底部收集得到干燥的超细颗粒的原料粉末;
S4:所述原料粉末在惰性气体的保护下高温烧结1~10h,烧结温度为600~850℃;
S5:最后冷却并粉碎,产品包装。
2.根据权利要求1所述锂电池磷酸钒锂电极活性材料的生产制备工艺方法,其特征在于:步骤S1中碳源为柠檬酸、蔗糖、葡萄糖、聚乙二醇、抗坏血酸或草酸氢铵。
3.根据权利要求1所述锂电池磷酸钒锂电极活性材料的生产制备工艺方法,其特征在于:步骤S1中碳源为抗坏血酸或草酸氢铵。
4.根据权利要求1~3任一所述锂电池磷酸钒锂电极活性材料的生产制备工艺方法,其特征在于:步骤S1中,首先将钒源溶于水得到五价钒溶液,然后继续加入碳源进行预反应得到三价钒溶液的前驱体,继续加入剩余计量的锂源和磷源,搅拌溶解;此过程中碳源加入的量的相对值范围为1.5≤y<1.8。
5.根据权利要求4所述锂电池磷酸钒锂电极活性材料的生产制备工艺方法,其特征在于:所述钒源为偏钒酸铵。
6.根据权利要求4所述锂电池磷酸钒锂电极活性材料的生产制备工艺方法,其特征在于:所述锂源为碳酸锂、氢氧化锂、醋酸锂或硝酸锂中的一种或多种的混合物。
7.根据权利要求4所述锂电池磷酸钒锂电极活性材料的生产制备工艺方法,其特征在于:所述磷源为磷酸二氢铵、磷酸氢二铵、磷酸铵或磷酸中的一种或多种的混合物。
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