CN103354288B - 一种改性磷酸铁锂正极材料制备方法 - Google Patents
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- 239000010405 anode material Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical class [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000000084 colloidal system Substances 0.000 claims abstract description 6
- 238000013019 agitation Methods 0.000 claims abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000001238 wet grinding Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 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
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 150000002642 lithium compounds Chemical class 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- 229910000583 Nd alloy Inorganic materials 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical class [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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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Abstract
本发明涉及一种锂离子电池正极材料的制备方法，按照以下工艺步骤实施：将锂化合物，Fe3+化合物，磷酸盐，还原剂和Er,Nd掺杂物按照摩尔比混合；所得混合物进行加热搅拌，形成胶体；然后将此胶体煅烧；所得物料放入球磨机中球磨、煅烧、自然冷却至室温得到掺杂型锂离子正极材料。本发明与现有技术相比，通过对磷酸铁锂正极材料进行改性，显著提高了材料的电导率，改善了低温性能和倍率放电性能。
Description
技术领域
本发明涉及一种锂离子电池正极材料的制备方法，特别适用于一种改性磷酸铁锂正极材料制备方法。
背景技术
目前现有技术，磷酸铁锂作为一种锂离子电池正极材料有其独特的优点：1相对较高的理论比容量170mAh/g；2好的热稳定性和化学稳定性；3低成本，低毒性和好的安全性能；4循环寿命长。但由于磷酸铁锂存在电导率低和锂离子传导率低的缺陷，从而导致电池的低温性能差和倍率放电性能差。
本发明的目的所要解决的技术问题是通过掺杂Er,Nd提高磷酸铁锂的电导率和锂离子传导率，从而改善其低温性能和倍率放电性能。
发明内容
本发明一种改性磷酸铁锂正极材料制备方法，其特征在于按照以下工艺步骤实施：
1.1将锂化合物，Fe3+化合物，磷酸盐，还原剂和Er,Nd掺杂物按照摩尔比混合，其中Li:Fe:P:Er:Nd=1:(1-x-y):1:x:y；0.02≥x≥0.01；0.02≥y≥0.01，将混合物溶于去离子水中；
1.2将步骤1所得混合物在55℃—85℃下进行加热搅拌，形成胶体，然后将此胶体置于300℃温度下煅烧3小时；
1.3将步骤2中所得物料放入球磨机中，加入湿磨介质，球磨时间8—12小时，将球磨好的粉末和适量的聚乙二醇混合好；
1.4将步骤3所得物料置于还原气氛或惰性气体下煅烧10—20小时，煅烧温度600—900℃，自然冷却至室温；
1.5将步骤4所得物料进行球磨，得到掺杂型锂离子正极材料LiFe1-x-yErxNdyPO4/C；其中：0.02≥x≥0.01,0.02≥y≥0.01。
本发明的一种改性磷酸铁锂正极材料制备方法，其特征在于所述掺杂物为Er,Nd的氧化物，氢氧化物，氯化物，硫酸盐，硝酸盐中至少一种。所述掺杂物Er,Nd的含量范围分别为0.02≥x≥0.01,0.02≥y≥0.01。
本发明所述锂化合物为碳酸锂，硝酸锂，氢氧化锂，醋酸锂和草酸锂中至少一种。本发明所述Fe3+化合物为硝酸铁。
本发明所述磷酸盐为磷酸铵，磷酸二氢铵，磷酸氢二铵中至少一种。本发明所述湿磨介质为无水乙醇，去离子水，丙酮中至少一种。
本发明与现有技术相比，通过对磷酸铁锂正极材料进行改性，显著提高了材料的电导率，改善了低温性能和倍率放电性能。
具体实施方式
实施例1
将0.1mol硝酸锂，0.1mol磷酸二氢铵，0.097mol硝酸铁，0.002molEr2O3,0.001molNd(Ac)3,混合。将混合物溶于去离子水中（混合物与去离子水质量比为1：（0.7~1.2）。并在80℃下搅拌4小时，至形成胶状物。将此胶状物置于300℃下煅烧3小时，将所得物质加入100ml无水乙醇进行球磨，球磨10小时。将球磨好的粉末与120ml聚乙二醇混合后置于氩气保护下，在700℃煅烧12小时。冷却至室温后，球磨得到所需粉料。以所得材料作为正极活性材料，Super-P做导电剂，PVDF做粘结剂。以上几种料以85：10：5的比例在NMP溶剂中(NMP:混合料=1：1.8重量比）混匀，然后涂布在铝箔上，干燥后，压制成极片。
硬碳和石墨以9：1的比例混合作为负极活性材料，Super-P作为导电剂，PVDF作粘结剂，以上物料以80：15：5的比例在NMP溶剂中(NMP:混合料=1：1.8重量比）混匀，然后涂布在铜箔上，干燥后，压制成极片。
电解液为1MLiPF6+EC/PC/DMC/PS/VC(10:40:45:3:2重量比)。
实施例2
同实施例1，只是Er2O3,Nd(Ac)3的量分别为0.001mol和0.001mol。
对比案例1（无Er,Nd加入）。
同实施例1，只是无Er,Nd加入。
测试结果
案例1-2及对比案例1的电池分别按照以下方法进行测试：
分别在25℃和在-20℃下，以1C放电，记录电池放电容量。测量电池容量保持率。结果如下表所示
| 案例1 | 案例2 | 对比案例1 | |
| 容量保持率 | 85.2% | 83.2% | 63.6% |
尽管对本发明的特征及其优势已经描述了很多，然而可以理解的是，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构想做其他多种相应的改变，而所有这些改变都应属于本发明的权利要求保护的范围。
Claims (2)
1.一种改性磷酸铁锂正极材料制备方法，其特征在于按照以下工艺步骤实施：
1.1将0.1mol硝酸锂，0.1mol磷酸二氢铵，0.097mol硝酸铁，还原剂，0.002molEr2O3,0.001molNd(Ac)3混合，将混合物溶于去离子水中；
1.2将步骤1所得混合物在55℃—85℃下进行加热搅拌，形成胶体，然后将此胶体置于300℃温度下煅烧3小时；
1.3将步骤2中所得物料放入球磨机中，加入湿磨介质，球磨时间8—12小时，将球磨好的粉末和适量的聚乙二醇混合；
1.4将步骤3所得物料置于还原气氛或惰性气体下煅烧10—20小时，煅烧温度600—900℃，自然冷却至室温；
1.5将步骤4所得物料进行球磨，得到掺杂型锂离子正极材料。
2.根据权利要求1所述的一种改性磷酸铁锂正极材料制备方法，其特征在于所述湿磨介质为无水乙醇，去离子水，丙酮中至少一种。
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Inventor after: Wang Jianli Inventor after: Ye Qing Inventor after: Lei Ruqing Inventor after: Xie Liuyang Inventor before: Wang Jianli Inventor before: Huang Zhiyi Inventor before: Lei Ruqing |
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Effective date of registration: 20171122 Address after: 437000 Xianning economic and Technological Development Zone (in the industrial park of the Yangtze River), Hubei Patentee after: Hubei dragon Nengxin energy Polytron Technologies Inc Address before: 437100 Hubei Xianning Economic Development Zone Changjiang Industrial Park Qinglong road can Lang Science Park Patentee before: Nengyilang Technology Co.,Ltd. |
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Effective date of registration: 20191205 Address after: 225321 diaopu Street Industrial Park, Gaogang District, Taizhou City, Jiangsu Province Patentee after: Li Qiannan Address before: 437000 Hubei Xianning economic and Technological Development Zone (Changjiang Industrial Park) Patentee before: Hubei dragon Nengxin energy Polytron Technologies Inc |
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Effective date of registration: 20191227 Address after: 343400 Ji'an City, Jiangxi province Yongxin County Industrial Development Zone Industrial Park Star Patentee after: Jiangxi Huahao new energy Co., Ltd Address before: 225321 diaopu Street Industrial Park, Gaogang District, Taizhou City, Jiangsu Province Patentee before: Li Qiannan |
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Denomination of invention: A preparation method of modified LiFePO4 cathode material Effective date of registration: 20201216 Granted publication date: 20160427 Pledgee: Yongxin County sub branch of Postal Savings Bank of China Ltd. Pledgor: Jiangxi Huahao new energy Co.,Ltd. Registration number: Y2020980009417 |
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