CN114655951A - 一种锂离子电池负极材料的制备方法 - Google Patents
一种锂离子电池负极材料的制备方法 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 title claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 57
- 239000010439 graphite Substances 0.000 claims abstract description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002131 composite material Substances 0.000 claims abstract description 52
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 32
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 238000001694 spray drying Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- YPDSOAPSWYHANB-UHFFFAOYSA-N [N].[F] Chemical compound [N].[F] YPDSOAPSWYHANB-UHFFFAOYSA-N 0.000 claims description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 10
- 238000004140 cleaning Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910021383 artificial graphite Inorganic materials 0.000 description 5
- 238000005056 compaction Methods 0.000 description 5
- -1 lithium titanate/graphite composites Chemical class 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 1
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 238000005096 rolling process Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
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- C01G23/00—Compounds of titanium
- C01G23/002—Compounds containing, besides titanium, two or more other elements, with the exception of oxygen or hydrogen
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Abstract
本发明公开了一种锂离子电池负极材料的制备方法,包括:将钛酸四丁酯分散于甘油溶剂中加入十六烷基三甲基溴化铵溶液,加四甲基氢氧化铵调节Ph;再添加氟化铵溶液,在150~200℃下加热1~6h,产物离心,清洗,真空干燥得到掺杂钛/氮/氟多孔二氧化钛;配置掺杂钛/氮/氟多孔二氧化钛有机溶液后添加锂盐溶液,再添加石墨,混合均匀,喷雾干燥,得到多孔钛酸锂包覆石墨复合材料;取多孔钛酸锂包覆石墨复合材料及氟化铵,置于管式炉在氩气保护下加热后升温到碳化即得。本发明能提升石墨复合材料的首次效率及其功率性能。
Description
技术领域
本发明属于锂离子电池材料技术领域,具体的说涉及一种锂离子电池负极材料的制备方法。
背景技术
随着锂离子电池对能量密度及其快充性能要求的提高,要求锂离子电池负极材料在具有高能量密度的同时,材料的快充性能也要得到提升。目前市场化的负极材料主要以人造石墨为主,实际比容量约为350-360mAh/g,充电倍率1C-5C,首次效率92-94%之间,无法满足下一代高能量密度快充电池的需求。为提升石墨材料的能量密度及其快充性能,一般是通过选取各向同性好,骨料粒径低及其包覆量多的无定形碳材料,但是对原料的选择提升幅度有限,及市场化的低阻抗原料基本筛选完毕并未明显降低阻抗,因此需要通过石墨内核的掺杂及其外壳包覆层的掺杂提升充放电过程中离子的扩散速率及其降低电子阻抗,改善功率性能;同时,掺杂包覆还可以改善材料的首次效率,间接提升电池的正极克容量发挥,并提升能量密度。而目前石墨材料掺杂包覆大多为无定形碳及其氮、硼及其导电剂、氧化物及其固体电解质等电子或离子导电性高的材料。比如中国专利申请号202011383817.3公开了一种石墨包覆材料及其制备方法,其电池负极是在石墨的表面包覆层中掺杂钽掺杂锂镧锆氧以及导电材料,可以有效提高锂离子的传输速率及扩散系数,从而使导电材料能够有效提高材料的电子导电率;外壳中的钽掺杂锂镧锆氧、无定形碳和导电材料协同表现出良好的锂离子导电率和电子导电性,有利于提升石墨包覆材料的离子传输速率和导电性,可有效提高石墨负极材料的倍率性能、安全性能和循环性能,但是存在首次效率偏低,功率性能改善不明显等缺陷。
发明内容
本发明的目的在于克服上述缺点而提供的一种能提升石墨复合材料的首次效率及其功率性能的锂离子电池负极材料的制备方法。
本发明的一种锂离子电池负极材料的制备方法,包括以下步骤:
(1)将钛酸四丁酯分散于甘油溶剂中配制成1~5wt%溶液,加入浓度为12g/L十六烷基三甲基溴化铵溶液,加四甲基氢氧化铵调节Ph为9-10,混合均匀;之后再添加1wt%氟化铵溶液,混合均匀后转移到水热反应釜中,在150~200℃下加热1~6h,产物离心,用乙醇、水清洗10次,置于真空干燥箱60℃干燥12h,得到掺杂钛/氮/氟多孔二氧化钛;
其中:钛酸四丁酯:十六烷基三甲基溴化铵:四甲基氢氧化铵:氟化铵的质量比为1:20~40:0.1~1:0.5~2;
(2)配置质量浓度为1~10wt%的掺杂钛/氮/氟多孔二氧化钛有机溶液,之后添加质量浓度为1~10wt%锂盐溶液,混合均匀后,再添加石墨,混合均匀,喷雾干燥,得到多孔钛酸锂包覆石墨复合材料;其中:掺杂钛/氮/氟多孔二氧化钛:锂盐:石墨的质量比为1~10:1~10:100;
(3)按照质量比100:1~10称取多孔钛酸锂包覆石墨复合材料及氟化铵,置于管式炉,其中氟化铵位于气流上游方向,并在氩气保护下在400℃加热2小时,之后升温到800℃碳化6h,得到氮、氟共钛酸锂/石墨复合材料即锂离子电池负极材料。
上述的一种锂离子电池负极材料的制备方法,其中所述步骤(2)中锂盐为碳酸锂、氢氧化锂、氯化锂、溴化锂、碘化锂或硫化锂中的一种。
本发明与现有技术相比,具有明显的有益效果,从以上技术方案可知:本发明首先通过对钛酸锂前驱体二氧化钛的氮、氟掺杂改善其阻抗及其降低其缺陷,为之后形成多孔钛酸锂提供基础;并在形成钛酸锂后再次对材料的氮、氟原子掺杂,减少形成钛酸锂过程中的缺陷,进一步改善钛酸锂的结构。这样通过在内核两次包覆含氮、氟原子得到多孔钛酸锂,并包覆在内核表面,从而提升石墨复合材料的首次效率及其功率性能。
附图说明
图1为实施例1得到的钛酸锂/石墨复合材料的SEM图;
具体实施方式
实施例1
一种锂离子电池负极材料的制备方法,包括以下步骤:
(1)将1g钛酸四丁酯分散于50ml甘油溶剂中配制成2wt%溶液,之后加入30ml,浓度为12g/L十六烷基三甲基溴化铵溶液(加0.5mL四甲基氢氧化铵调节pH=9),混合均匀;之后再添加100g,1wt%氟化氨溶液,混合均匀后转移到水热反应釜中,在180℃下加热3h;产物离心(1000r/min,1h),用乙醇、水依次清洗10次,置于真空干燥箱60℃干燥12h,得到掺杂钛/氮/氟多孔二氧化钛;
(2)将5g掺杂钛/氮/氟多孔二氧化钛添加到100ml四氯化碳溶液中配置质量浓度为5wt%的掺杂钛/氮/氟多孔二氧化钛溶液,之后添加100ml,质量浓度为5wt%碳酸锂溶液,混合均匀后,再添加100g人造石墨,混合均匀,喷雾干燥,得到多孔钛酸锂包覆石墨复合材料;
(3)称取100g多孔钛酸锂包覆石墨复合材料及5g氟化铵,置于管式炉,其中氟化铵位于气流上游方向,并在氩气保护下在400℃加热2小时,之后升温到800℃碳化6h,得到氮、氟共掺杂钛酸锂/石墨复合材料即锂离子电池负极材料。
实施例2
一种锂离子电池负极材料的制备方法,包括以下步骤:
(1)将1g钛酸四丁酯分散于100ml甘油溶剂中配制成1wt%溶液,加入20ml,浓度为12g/L十六烷基三甲基溴化铵溶液(加0.1ml四甲基氢氧化铵调节pH),混合均匀;之后再添加50ml,1wt%氟化氨溶液,混合均匀后转移到水热反应釜中,在150℃下加热6h;产物离心(1000r/min,1h),用乙醇、水依次清洗10次,置于真空干燥箱60℃干燥12h,得到掺杂钛/氮/氟多孔二氧化钛;
(2)将1g掺杂钛/氮/氟多孔二氧化钛添加到100ml四氯化碳溶液中配置质量浓度为1wt%的掺杂钛/氮/氟多孔二氧化钛溶液,之后添加100ml,质量浓度为1wt%氢氧化锂溶液,混合均匀后,再添加100g人造石墨,混合均匀,喷雾干燥,得到多孔钛酸锂包覆石墨复合材料;
(3)称取100g多孔钛酸锂包覆石墨复合材料及1g氟化铵,置于管式炉,其中氟化铵位于气流上游方向,并在氩气保护下在400℃加热2小时,之后升温到800℃碳化6h,得到氮、氟共掺杂钛酸锂/石墨复合材料即锂离子电池负极材料。
实施例3
一种锂离子电池负极材料的制备方法,包括以下步骤:
(1)将1g钛酸四丁酯分散于20ml甘油溶剂中配制成5wt%溶液,加入40ml,浓度为12g/L十六烷基三甲基溴化铵溶液(加1ml四甲基氢氧化铵调节pH),混合均匀;之后再添加200ml,1wt%氟化氨溶液,混合均匀后转移到水热反应釜中,在200℃下加热1h;产物离心(1000r/min,1h),用乙醇、水依次清洗10次,置于真空干燥箱60℃干燥12h,得到掺杂钛/氮/氟多孔二氧化钛;
(2)将10g掺杂钛/氮/氟多孔二氧化钛添加到100ml四氯化碳溶液中配置质量浓度为10wt%的掺杂钛/氮/氟多孔二氧化钛溶液,之后添加100ml,10wt%氯化锂溶液,混合均匀后,再添加100g人造石墨,混合均匀,喷雾干燥,得到多孔钛酸锂包覆石墨复合材料;
(3)按照质量比100:1~10称取100g多孔钛酸锂包覆石墨复合材料及10g氟化铵,置于管式炉,其中氟化铵位于气流上游方向,并在氩气保护下在400℃加热2小时,之后升温到800℃碳化6h,得到氮、氟共掺杂钛酸锂/石墨复合材料即锂离子电池负极材料。
对比例
将5g酚醛树脂添加到100ml四氯化碳溶液中配置质量浓度为5wt%的树脂溶液,之后再添加100g人造石墨,混合均匀,喷雾干燥,得到硬碳包覆石墨复合材料B;之后升温到800℃碳化6h,得到石墨复合材料。
1.理化性能测试
1.1SEM测试
将实施例1中制得的钛酸锂/石墨复合材料进行SEM测试,测试结果如图1所示。由图1中可以看出,实施例1制得的复合材料呈现颗粒状,大小分布均匀,其粒径介于8~15μm之间。
1.2粉体电导率测试:
将粉体压制成块状结构,之后采用四探针测试仪测试其粉体的电阻率。测试结果如表1所示。
1.3粉体压实密度测试
对实施例1-3和对比例制备的复合材料进行粉体压实密度测试。测试时,称取一定质量的粉体放置到模具中,采用2T的压力压制(采用粉体压实密度仪,将1g粉体放置到固定的釜中之后采用2T压力压制,静止10S,之后计算压制下的体积大小,并计算出压实密度),计算出粉体压实密度。测试结果如表1所示。
表1
由表1可以看出,实施例1-3制得的石墨复合材料的粉体电阻率明显小于各对比例。其原因为材料表面包覆氮、氟提升材料的压实密度及其氮降低材料的电子阻抗。同时多孔结构提升材料的比表面积。
2.扣式电池测试
分别将实施例1-3和对比例中的钛酸锂/石墨复合材料组装成扣式电池A1、A2、A3、B1。组装方法为:在负极材料中添加粘结剂、导电剂及溶剂,进行搅拌制浆,涂覆在铜箔上,经过烘干、碾压制得负极片。所用粘结剂为LA132粘结剂,导电剂为SP,负极材料分别为实施例1-3和对比例中的钛酸锂/石墨复合材料,溶剂为二次蒸馏水。各组分的比例为:负极材料:SP:LA132:二次蒸馏水=95g:1g:4g:220mL;电解液是LiPF6/EC+DEC(LiPF6的浓度为1.2mol/L,EC和DEC体积比为1:1),金属锂片为对电极,隔膜采用聚乙烯(PE),聚丙烯(PP)或聚乙丙烯(PEP)复合膜。扣式电池的装配在充氩气的手套箱中进行,电化学性能测试在武汉蓝电CT2001A型电池测试仪上进行,充放电电压范围为0.005V至2.0V,充放电倍率为0.1C。测试结果如表2所示。
同时取上述负极片,测试极片的吸液保液能力,结果见表2。
表2实施例与对比例的扣式电池及其极片吸液性能比较
项目 | 首次放电容(mAh/g) | 首次效率(%) | 吸液能力(mL/min) |
实施例1/A1 | 361.3 | 97.3 | 9.8 |
实施例2/A2 | 359.4 | 96.9 | 9.3 |
实施例3/A3 | 359.5 | 96.7 | 8.8 |
对比例1/B1 | 352.4 | 92.2 | 3.4 |
从表2可以看出,采用实施例1-3所得石墨复合负极材料的锂离子电池的首次放电容量及首次充放电效率、吸液能力均明显高于对比例。其原因为,实施例高的比表面积提升极片的吸液性能,同时外层的钛酸锂降低其不可逆损失,提升首次效率。
3.软包电池测试
以实施例1-3和对比例中的石墨复合材料作为负极材料,制备出负极极片。以三元材料(LiNi1/3Co1/3Mn1/3O2)为正极,以LiPF6溶液(溶剂为EC+DEC,体积比1:1,LiPF6浓度1.3mol/L)为电解液,celegard2400为隔膜,制备出2Ah软包电池A10、A20、A30和B10,B20。之后测试软包电池的循环性能、倍率性能。
倍率性能测试条件:充电倍率:1C/2C/3C/5C,放电倍率1C;电压范围:2.8-4.2V。
循环测试条件为,1C/1C,2.8-4.2V,温度:25±3℃,循环次数,500周。
测试结果见表3。
表3、实施例与对比例的恒流比和循环性能比较
由表3可以看出,本发明实施例1-3制备的钛酸锂/石墨复合材料制备的软包电池具有更好的恒流比,对比例的恒流比显著下降。因为在实施例材料表面包覆锂离子导电率的多孔钛酸锂提升离子传输速率,氮、氟提升材料的电子传输速率,从而提升电池的倍率性能,同时多孔钛酸锂具有层间距大,结构稳定的特性提升材料的循环性能。
以上仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (2)
1.一种锂离子电池负极材料的制备方法,包括以下步骤:
(1)将钛酸四丁酯分散于甘油溶剂中配制成1~5wt%溶液,加入浓度为12g/L十六烷基三甲基溴化铵溶液,加四甲基氢氧化铵调节Ph为9-10,混合均匀;之后再添加1wt%氟化铵溶液,混合均匀后转移到水热反应釜中,在150~200℃下加热1~6h,产物离心,用乙醇、水清洗10次,置于真空干燥箱60℃干燥12h,得到掺杂钛/氮/氟多孔二氧化钛;
其中:钛酸四丁酯:十六烷基三甲基溴化铵:四甲基氢氧化铵:氟化铵的质量比为1:20~40:0.1~1:0.5~2;
(2)配置质量浓度为1~10wt%的掺杂钛/氮/氟多孔二氧化钛有机溶液,之后添加质量浓度为1~10wt%锂盐溶液,混合均匀后,再添加石墨,混合均匀,喷雾干燥,得到多孔钛酸锂包覆石墨复合材料;其中:掺杂钛/氮/氟多孔二氧化钛:锂盐:石墨的质量比为1~10:1~10:100;
(3)按照质量比100:1~10称取多孔钛酸锂包覆石墨复合材料及氟化铵,置于管式炉,其中氟化铵位于气流上游方向,并在氩气保护下在400℃加热2小时,之后升温到800℃碳化6h,得到氮、氟共钛酸锂/石墨复合材料。
2.如权利要求1所述的一种锂离子电池负极材料的制备方法,其中所述步骤(2)中锂盐为碳酸锂、氢氧化锂、氯化锂、溴化锂、碘化锂或硫化锂中的一种。
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CN102683705A (zh) * | 2012-04-24 | 2012-09-19 | 合肥国轩高科动力能源有限公司 | 一种钛酸锂包覆改性的石墨复合负极材料及其制备方法与应用 |
US20160049692A1 (en) * | 2013-03-27 | 2016-02-18 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery |
JP2015079727A (ja) * | 2013-09-10 | 2015-04-23 | 東レ株式会社 | リチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極材料の製造方法、リチウムイオン二次電池負極用樹脂組成物、リチウムイオン二次電池用負極、および、リチウムイオン二次電池 |
CN106374093A (zh) * | 2016-11-07 | 2017-02-01 | 珠海格力电器股份有限公司 | 石墨复合材料、其制备方法与应用 |
CN107959010A (zh) * | 2017-11-14 | 2018-04-24 | 中航锂电(洛阳)有限公司 | 一种石墨复合材料及其制备方法 |
CN111969185A (zh) * | 2020-07-07 | 2020-11-20 | 湖南大学 | 包覆TiO2的石墨双离子电池复合正极材料及其制备方法 |
CN112018366A (zh) * | 2020-09-10 | 2020-12-01 | 安徽科达新材料有限公司 | 一种锂离子电池石墨负极材料及其制备方法 |
CN113937257A (zh) * | 2021-08-27 | 2022-01-14 | 山东大学 | 氮、氟共掺杂二氧化钛/碳微米球材料及其制备方法与在钠离子电池中的应用 |
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US20230331577A1 (en) | 2023-10-19 |
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