CN108155361B - 一种磷酸锂铁电池 - Google Patents
一种磷酸锂铁电池 Download PDFInfo
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 229910052493 LiFePO4 Inorganic materials 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000006258 conductive agent Substances 0.000 claims abstract description 10
- 229910010710 LiFePO Inorganic materials 0.000 claims abstract description 9
- 239000011149 active material Substances 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- 239000002033 PVDF binder Substances 0.000 claims abstract description 4
- 239000006230 acetylene black Substances 0.000 claims abstract description 4
- 239000003792 electrolyte Substances 0.000 claims abstract description 4
- 239000012982 microporous membrane Substances 0.000 claims abstract description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 229910001290 LiPF6 Inorganic materials 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 229930182470 glycoside Natural products 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- -1 alkyl glycoside Chemical class 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 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 7
- 150000004677 hydrates Chemical class 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 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 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229910021586 Nickel(II) chloride 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 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229960004887 ferric hydroxide Drugs 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 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
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- 229910000904 FeC2O4 Inorganic materials 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 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 description 6
- 239000008103 glucose Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 229920000858 Cyclodextrin Polymers 0.000 description 3
- 239000001116 FEMA 4028 Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 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 description 3
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 3
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 3
- 229960004853 betadex Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010701 LiFeP Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- PYIDGJJWBIBVIA-UYTYNIKBSA-N lauryl glucoside Chemical compound CCCCCCCCCCCCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O PYIDGJJWBIBVIA-UYTYNIKBSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- 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
- H01M4/362—Composites
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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
-
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- C01—INORGANIC CHEMISTRY
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- 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
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- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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Abstract
本发明涉及一种磷酸锂铁电池,所述磷酸锂铁电池的制备方法包括如下步骤:以PVDF为粘结剂,乙炔黑为导电剂,以上述的LiFePO4/C复合材料为活性材料,按上述的LiFePO4/C复合材料、导电剂和粘结剂质量比为8:1:1,用NMP调浆,以1M的LiPF6/(EC:DMC=1:1)为电解液,FE/PC/PE三层复合微孔膜为隔膜。
Description
技术领域
本发明属于材料领域,具体涉及一种磷酸锂铁电池。
背景技术
锂离子电池广泛用于手机、笔记本电脑、摄像机等便携式电子设备中,日益扩大的电动汽车领域将给锂离子电池带来更大的发展空间。橄榄石结构的LiFePO4材料具有来源广泛、比容量高、循环性能良好、安全性能突出、对环境友好等优点,被视为最有前途的锂离子电池正极材料之一,受到了人们的广泛关注。然而对于高负载水平的大电池而言,如电动汽车电池,在正极材料的成本、充放电效率、安全性能等方面还存在着问题,刺激了人们对正极材料LiFePO4的研究。LiFePO4作为锂离子正极材料,其充放电机理不同于其他传统的过渡金属氧化物(如:LiCoO2等),室温下锂离子在LiFePO4中的脱嵌过程是一个两相反应,存在着LiFePO4和FePO4两种物相之间的转化。由于在LiFePO4晶体结构中,FeO6八面体共顶点而非共边,这一结构降低了电子导电率,使得即使在室温条件下锂离子的迁移速率也很小,所以LiFePO4其固有的晶体结构限制了其电导性与锂离子扩散性能。因此,迫切需要寻求一种改性的LiFePO4材料。
烷基糖苷(APG)具有诸多优点,被广泛用于洗涤剂、食品、农药、生物、化工等领域,本发明首次将其作为碳源前驱体,用于替代葡萄糖、β-环糊精等,使得镍掺杂的LiFePO4/C复合材料的充放电比容量和循环性能得到了很大提高。
发明内容
本发明提供一种镍掺杂改性的LiFePO4/C复合材料的制备方法,其特征在于包括如下步骤:
(1)将磷源、铁源、锂源、镍源置于球磨罐中,加入碳源前驱体和分散剂后,进行球磨,得浆料;
(2)将步骤(1)球磨得到的浆料干燥、研磨成粉末后,于700-800℃下煅烧,冷却后即得LiFePO4/C复合材料。
步骤(1)所述的磷源选自磷酸二氢铵,铁源选自草酸亚铁、氢氧化铁、硝酸铁或它们的水合物中的一种或几种,锂源选自碳酸锂、氢氧化锂或它们的水合物中的一种或几种、镍源选自硝酸镍、氯化镍或它们的水合物中的一种或几种,或者磷源和锂源一起选自磷酸二氢锂,磷源、铁源、锂源、镍源的摩尔用量按照其中磷元素:铁元素:锂元素:镍元素的摩尔比为1:1:1:0.02-0.04;碳源前驱体选自烷基糖苷;分散剂选自乙醇;所述球磨优选采用行星式球磨机以600-700r/min的自转速度球磨5-6h;
步骤(2)所述煅烧时间为8-12h。
本发明的另一实施方案提供上述LiFePO4/C复合材料作为锂电池正极材料的应用。
本发明的另一实施方案提供一种锂电池,其特征在于包含上述的LiFePO4/C复合材料,作为活性材料。
本发明的另一实施方案提供一种磷酸锂铁电池,其特征在于所述磷酸锂铁电池的制备方法包括如下步骤:以PVDF为粘结剂,乙炔黑为导电剂,以上述的LiFePO4/C复合材料为活性材料,按上述的LiFePO4/C复合材料、导电剂和粘结剂质量比为8:1:1,用NMP调浆,以1M的LiPF6/(EC:DMC=1:1)为电解液,FE/PC/PE三层复合微孔膜为隔膜。
本发明所述的烷基糖苷是指普通商业化烷基糖苷(简称APG),常用作表面活性剂,由葡萄糖和脂肪醇合成。进一步地所述的烷基糖苷优选烷基单糖苷(通式为ROG,其中R为C8-C16直链烷基,G为葡萄糖)。
与现有技术相比,本发明的优点在于:(1)采用镍元素掺杂提高LiFePO4/C复合材料的性能,并对公开了镍元素的最佳掺杂用量;(2)使用烷基糖苷APG作为碳源替代葡萄糖或β-环糊精,提高了LiFePO4/C复合材料的性能。
附图说明
图1是产品A的SEM图
图2是产品A、B的IR图
具体实施方式
为了便于对本发明的进一步理解,下面提供的实施例对其做了更详细的说明。但是这些实施例仅供更好的理解发明而并非用来限定本发明的范围或实施原则,本发明的实施方式不限于以下内容。
实施例1
分别称取50mmol NH4H2PO4、50mmol FeC2O4·2H2O、25mmol Li2CO3、1mmol Ni(NO3)2加入氧化锆球磨罐中,再加入3.2g烷基糖苷(APG)作为碳源前驱体,以乙醇为分散剂,采用行星式球磨机以600r/min的转速球磨5h,收集浆料干燥,并用玛瑙研钵研磨成粉末,放入马弗炉中于700℃下焙烧12h后,冷却得镍掺杂改性的LiFePO4/C复合材料(以下简称产品A)。
实施例2
分别称取50mmol NH4H2PO4、50mmol FeC2O4·2H2O、50mmol LiOH、2mmol NiCl2加入氧化锆球磨罐中,再加入3.2g十二烷基葡糖苷作为碳源前驱体,以乙醇为分散剂,采用行星式球磨机以700r/min的转速球磨5h,收集浆料干燥,并用玛瑙研钵研磨成粉末,放入马弗炉中于800℃下焙烧8h后,冷却得镍掺杂改性的LiFePO4/C复合材料(以下简称产品B)。
实施例3
分别称取50mmol NH4H2PO4、50mmol FeC2O4·2H2O、25mmol Li2CO3、1mmol Ni(NO3)2加入氧化锆球磨罐中,再加入3.2g葡萄糖作为碳源前驱体,以乙醇为分散剂,采用行星式球磨机以600r/min的转速球磨5h,收集浆料干燥,并用玛瑙研钵研磨成粉末,放入马弗炉中于700℃下焙烧12h后,冷却得镍掺杂改性的LiFePO4/C复合材料(以下简称产品C)。
实施例4
分别称取50mmol NH4H2PO4、50mmol FeC2O4·2H2O、25mmol Li2CO3、1mmol Ni(NO3)2加入氧化锆球磨罐中,再加入3.2gβ-环糊精作为碳源前驱体,以乙醇为分散剂,采用行星式球磨机以600r/min的转速球磨5h,收集浆料干燥,并用玛瑙研钵研磨成粉末,放入马弗炉中于700℃下焙烧12h后,冷却得镍掺杂改性的LiFePO4/C复合材料(以下简称产品D)。
实施例5
分别称取50mmol NH4H2PO4、50mmol FeC2O4·2H2O、25mmol Li2CO3、0.5mmol Ni(NO3)2加入氧化锆球磨罐中,再加入3.2g烷基糖苷(APG)作为碳源前驱体,以乙醇为分散剂,采用行星式球磨机以600r/min的转速球磨5h,收集浆料干燥,并用玛瑙研钵研磨成粉末,放入马弗炉中于700℃下焙烧12h后,冷却得镍掺杂改性的LiFePO4/C复合材料(以下简称产品E)。
实施例6
分别称取50mmol NH4H2PO4、50mmol FeC2O4·2H2O、25mmol Li2CO3、5mmol Ni(NO3)2加入氧化锆球磨罐中,再加入3.2g烷基糖苷(APG)作为碳源前驱体,以乙醇为分散剂,采用行星式球磨机以600r/min的转速球磨5h,收集浆料干燥,并用玛瑙研钵研磨成粉末,放入马弗炉中于700℃下焙烧12h后,冷却得镍掺杂改性的LiFePO4/C复合材料(以下简称产品F)。
实施例7
分别称取50mmol NH4H2PO4、50mmol FeC2O4·2H2O、25mmol Li2CO3加入氧化锆球磨罐中,再加入3.2g烷基糖苷(APG)作为碳源前驱体,以乙醇为分散剂,采用行星式球磨机以600r/min的转速球磨5h,收集浆料干燥,并用玛瑙研钵研磨成粉末,放入马弗炉中于700℃下焙烧12h后,冷却得LiFePO4/C复合材料(以下简称产品G)。
实施例8
分别称取50mmol NH4H2PO4、50mmol FeC2O4·2H2O、25mmol Li2CO3加入氧化锆球磨罐中,再加入3.2g葡萄糖作为碳源前驱体,以乙醇为分散剂,采用行星式球磨机以600r/min的转速球磨5h,收集浆料干燥,并用玛瑙研钵研磨成粉末,放入马弗炉中于700℃下焙烧12h后,冷却得LiFePO4/C复合材料(以下简称产品H)。
实施例9产品A-H的性能测试
以PVDF为粘结剂,乙炔黑为导电剂,按活性材料(产品A-H)、导电剂和粘结剂质量比为8:1:1,用NMP调浆,以1M的LiPF6/(EC:DMC=1:1)为电解液,FE/PC/PE三层复合微孔膜为隔膜。采用深圳新威公司的电池测试系统(Newware,CT-3008,China)对组装好的纽扣电池在室温下进行恒电流充放电测试(表1),充放电测试的电压范围为2.5~4.2V。
表1产品产品A-H在0.1C倍率下的充放电性能
由以上测试结果,可以看出本发明产品A、B的充放电比容量和循环性能最好,这表明碳源前驱体——烷基糖苷和镍掺杂对提高LiFePO4/C复合材料的性能起到重要作用,尤其是镍元素的用量在0.02-0.04时最佳。
Claims (5)
1.一种镍掺杂改性的LiFePO4/C复合材料的制备方法,包括如下步骤:
(1)将磷源、铁源、锂源、镍源置于球磨罐中,加入碳源前驱体和分散剂后,进行球磨,得浆料;
(2)将步骤(1)球磨得到的浆料干燥、研磨成粉末后,于700-800℃下煅烧,冷却后即得所述LiFePO4/C复合材料;
步骤(1)所述的磷源选自磷酸二氢铵,铁源选自草酸亚铁、氢氧化铁、硝酸铁或它们的水合物中的一种或几种,锂源选自碳酸锂、氢氧化锂或它们的水合物中的一种或几种,镍源选自硝酸镍、氯化镍或它们的水合物中的一种或几种,或者磷源和锂源一起选自磷酸二氢锂,磷源、铁源、锂源、镍源的摩尔用量按照其中磷元素:铁元素:锂元素:镍元素的摩尔比为1:1:1:0.02-0.04;碳源前驱体选自烷基糖苷;分散剂选自乙醇。
2.权利要求1所述的制备方法,其特征在于步骤(1)所述球磨采用行星式球磨机以600-700r/min的自转速度球磨5-6h。
3.权利要求1所述的制备方法,其特征在于步骤(2)所述煅烧时间为8-12h。
4.一种锂电池,其特征在于包含权利要求1-3任一项所述方法制备的LiFePO4/C复合材料作为活性材料。
5.一种磷酸锂铁电池,其特征在于其制备方法包括如下步骤:以PVDF为粘结剂,乙炔黑为导电剂,以权利要求1-3任一项所述方法制备的LiFePO4/C复合材料为活性材料,按LiFePO4/C复合材料:导电剂:粘结剂质量比为8:1:1,用NMP调浆,以1M的LiPF6/(EC:DMC=1:1)为电解液,FE/PC/PE三层复合微孔膜为隔膜。
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