CN1102805C - 溶胶－凝胶法制备锂二次电池正极材料LiCrxMn2－xO4的新方法 - Google Patents
溶胶－凝胶法制备锂二次电池正极材料LiCrxMn2－xO4的新方法 Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 11
- 238000003980 solgel method Methods 0.000 title claims description 7
- 239000007774 positive electrode material Substances 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000084 colloidal system Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 4
- 229910001960 metal nitrate Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 abstract description 24
- 239000011651 chromium Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 10
- 229910052804 chromium Inorganic materials 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 229910015645 LiMn Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 229910012820 LiCoO Inorganic materials 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming Methods 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
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- H01M10/052—Li-accumulators
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
本发明涉及溶胶-凝胶法制备锂二次电池正极材料LiCrxMn2-xO4(0＜x＜0.3)的新方法，用于锂二次电池的正极材料及制备方法，这种材料为掺铬锂锰复合氧化物LiCrxMn2-xO4(0＜x＜0.3)。溶胶-
凝胶三步合成法制备这种材料的步骤是：将所用金属的硝酸盐按Li∶Mn∶Cr(原子比)＝1～1.05∶2-
X∶X的比溶于柠檬酸的乙二醇溶液中制成胶体，再经60～180℃真空干燥、200～300℃热分解后于500～800℃热处理6～12小时。该产物用于锂二次电池的正极
材料，具有比容量高、循环性能优良等特点，其充放电循环前十次放电的平均比容量高达128mAh/g，完全可以和LiCoO2相媲美，但成本非常低
。
Description
一、技术领域
本发明属于能源技术领域，特别涉及锂二次电池正极材料掺铬锂锰复合氧化物LiCrxMn2-
xO4(0＜x＜0.3)的制备方法，利用此法制得的电极材料具有容量高、循环性能好等特点。
二、背景技术
锂二次电池正极材料LiMn2O4具有高容量、低成本、低污染等显著的优点，被认为是继LiCoO2之后首选的正极材料，但其较差的循环性限制了其应用。LiGuohua等(J.Electrochem
.Soc.，143(1)，178，1996)采用掺杂Co、Cr、Ni改善了LiMn2O4的循环性能。他们以Li2CO3、Mn(CHCOO
)2·4H2O及Cr2O3为原料，在600℃下预处理6小时后，于750℃合成3天制得了LiCrxMn2-
xO4(0＜x＜0.33)。Robertson等(J.Electrochem.Soc.，144(10)，3500，1997)用混合的计量氧化物、碳酸盐或氢氧化物直接在控制气氛下于800℃煅烧20～45小时制得了循环可逆容量达110mAh/g的低掺杂正极材料LiCr0.02Mn1.98O4。最近，D.Zha
ng等(J.PowerSources 76，81，1998)采用高压固态反应制备了LiCrxMn2-
xO4，其比容量也超过了110mAh/g。虽然这些文献中合成的LiCrxMn2-
xO4都具有较高比容量与优良的循环性能，但由于都采用固态反应，原料混合不均匀，热合成温度过高，合成时间过长，易造成产物缺陷，影响其比容量与循环性能。
三、发明内容
本发明的目的是克服现有技术中的缺点，采用能在原子水平上混合的溶胶-凝胶法制备出高容量、优良循环性能的正极材料LiCrxMn2-
xO4(0＜x＜0.3)。
本发明中正极材料LiCrxMn2-
xO4(0＜x＜0.3)化合物的制备方法为：将所用金属的硝酸盐按Li∶Mn∶Cr(原子比)＝1～1.05∶2-
X∶X的比溶于柠檬酸的乙二醇溶液中制成胶体，再经60～180℃真空干燥、200～300℃热分解、500～800℃热处理6～12小时。
采用双电极式Swagelock模拟电池对LiCoO2、LiMn2O4、Li
CrxMn2-xO4(固态法)以及本发明的掺铬锂锰复合氧化物进行性能测试，电池的正极材料组成如下：75～90％正极活性材料，10～15％导电剂乙炔黑，5～10％的粘结剂聚四氟乙烯乳液。电池的负极为锂片，电解液为1M LiPF6的1∶1碳酸乙烯酯(EC)-碳酸二乙酯(DEC)溶液，隔膜为Cellgard2500微孔隔膜。
四、附图说明
图1为Li/LiCoO2电池的循环性能曲线；
图2为Li/LiMn2O4电池的循环性能曲线；
图3为Li/LiCr0.1Mn1.9O4(固态法)电池的循环性能曲线；
图4为Li/LiCr0.05Mn1.95O4(溶胶-
凝胶法)电池的循环性能曲线。
五、具体实施方式
下面通过实例对比显示本发明专利的有利效果。
例1
将日本进口LiCoO2正极材料按前述制成薄片进行性能测试，典型极片重量为15～20mg，直径1cm，在4.25～2.75V电压范围内以0.2mA/cm2的电流恒流充放。测试结果如图1所示，该图显示了Li/LiCoO2电池的循环性能。
例2
将Li2CO3与MnCO3按Li∶Mn(原子比)＝1∶2的比例充分混合，置
于瓷坩埚内，在空气中于600℃预处理6小时，然后于750℃下加热48小时。所得产物按前述制成正极薄片进行充放电测试，典型极片重量15～20mg，直径1cm，以0.2mA/cm2的电流恒流充放，电压范围4.3～3.35V。测试结果如图2所示，该图显示了Li/LiMn2O4电池的循环性能。
例3
按Li Guohua等(J.Electrochem.Soc.，143(1)，178，1996)的固态法合成LiCrxMn2-xO4，所得产物按前述制成正极薄片进行充放电测试，典型极片重量15～20mg，直径1cm，以0.2mA/cm2的电流恒流充放，电压范围4.3～3.35V。测试结果如图3所示，该图显示了Li/LiCr0.1Mn1.9O4(固态法)电池的循环性
能。
例4
将硝酸锂、硝酸锰与硝酸铬按Li∶Mn∶Cr(原子比)＝1∶2-X∶X的比溶于柠檬酸的乙二醇溶液中制成胶体，于140℃蒸除过量溶剂后经180℃真空干燥制成前体物，将前体物研磨后置于瓷坩埚内，在空气中于300℃热分解，然后于600℃热处理8小时。所得产物按前述制成正极薄片进行充放电测试，条件同例2。测试结果如图4所示，该图显示了Li/LiCr0.05Mn1.95O4(溶胶-
凝胶法)电池的循环性能。
上述各实例的测试结果对比在下表中示出。从表中可以看出，采用本发明[例4]制备的掺铬锂锰复合氧化物与LiCoO2相比具有相近的比容量；与LiCrxMn2-
xO4(固态法)相比，其比容量明显提高，且循环性能优良。因此，用本发明制备的掺铬锂锰复合氧化物完全可以取代LiCoO2作为锂二次电池的正极材料。
表1 各种材料前十次的充放电性能对照表
| 实例编号 | 正极材料 | 平均比容量(mAh/g) | 平均容量衰减(mAh/循环) |
| 1 | LiCoO2 | 120 | 3 |
| 2 | LiMn2O4 | 97 | 5 |
| 3 | LiCr0.1Mn1.9O4 | 115 | 0.4 |
| 4 | LiCr0.05Mn1.95O4 | 128 | 0.5 |
本发明的有益效果：
采用本发明溶胶-
凝胶法制备的新材料其充放电循环性能优良，其前十次放电平均比容量达128mAh/g，可以与LiCoO2材料相媲美，但其成本相对却便宜的多。
Claims (1)
1.一种溶胶—凝胶法制备锂二次电池正极材料LiCrxMn2-xO4的方法，其特征是：
(1)将金属硝酸盐按原子比Li∶Mn∶Cr＝1～1.05∶2-X∶X的比例溶于柠檬酸的乙二醇溶液中制成胶体，其中0＜X＜0.3；
(2)经60～180℃真空干燥；
(3)200～300℃热分解；
(4)500～800℃热处理6～12小时制得。
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| CN99111152A CN1102805C (zh) | 1999-07-28 | 1999-07-28 | 溶胶－凝胶法制备锂二次电池正极材料LiCrxMn2－xO4的新方法 |
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| CN99111152A CN1102805C (zh) | 1999-07-28 | 1999-07-28 | 溶胶－凝胶法制备锂二次电池正极材料LiCrxMn2－xO4的新方法 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5169736A (en) * | 1990-08-09 | 1992-12-08 | Varta Batterie Aktiengesellschaft | Electrochemical secondary element |
| US5783333A (en) * | 1996-11-27 | 1998-07-21 | Polystor Corporation | Lithium nickel cobalt oxides for positive electrodes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5169736A (en) * | 1990-08-09 | 1992-12-08 | Varta Batterie Aktiengesellschaft | Electrochemical secondary element |
| US5783333A (en) * | 1996-11-27 | 1998-07-21 | Polystor Corporation | Lithium nickel cobalt oxides for positive electrodes |
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