CN1095599C - 高性能锂离子电池正极材料LiMn2O4的制备方法 - Google Patents
高性能锂离子电池正极材料LiMn2O4的制备方法 Download PDFInfo
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- CN1095599C CN1095599C CN97109010A CN97109010A CN1095599C CN 1095599 C CN1095599 C CN 1095599C CN 97109010 A CN97109010 A CN 97109010A CN 97109010 A CN97109010 A CN 97109010A CN 1095599 C CN1095599 C CN 1095599C
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000010405 anode material Substances 0.000 title 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 10
- 239000010406 cathode material Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 238000003825 pressing Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 229910015645 LiMn Inorganic materials 0.000 claims 1
- 239000011656 manganese carbonate Substances 0.000 claims 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- 229910012851 LiCoO 2 Inorganic materials 0.000 abstract description 6
- 229910013553 LiNO Inorganic materials 0.000 abstract description 4
- 239000007774 positive electrode material Substances 0.000 abstract description 4
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- -1 LiCoO 2 Chemical class 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- H01M4/48—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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种高性能锂离子电池正极材料LiMn2O4的制备方法。它是以MnO2、MnCO3、Mn(NO3)2或Mn(CH3COO)2和LiOH、Li2CO3或LiNO3为原料，按锂/锰摩尔比为0.45～0.5的比例混合并压成块状后在高温下合成的。由本发明得到LiMn2O4材料电性能达到120mAh/g比容量。工作电位在4.15～3.7伏，而成本仅为LiCoO2材料的4.5%。LiMn2O4是先进的锂离子电池首选的正极材料。
Description
技术领域
本发明涉及一种高性能锂离子电池正极材料的制备方法，它属于电化学、无机合成和电子产品技术领域。
背景技术
锂离子电池是近几年脱颖而出的最新一代高比能量化学电源，它一出现以其强大生命力广泛用于移动通讯、便携式手提计算机、摄像机、照像机、便携式仪器仪表等领域，也是各国大力研究的电动汽车首选配套电源。在锂离子电池发展和制造过程中，正极材料制备是关键技术之一。各国研究机构和电池制造厂家都投入大量人力、物力研制各种具有容量大、电位高的正极材料，研究最多的是以过渡金属为主的氧化物，如LiCoO2、LiNiO2、LiMn2O4，LiCoO2材料已是成熟产品，在日本已有广泛应用。但LiCoO2材料价格偏高，进口成品材料1200～1600元/Kg，以它作正极材料制造的锂离子电池价格昂贵，使得应用范围受到一定限制。LiNiO2和LiMn2O4不仅具有与LiCoO2相当的电化学性能，而且具有明显的价格优势，LiMn2O4比LiNiO2价格更低，更具应用前景。因而倍受各国电化学行业的关注，是目前锂离子电池正极材料研究的热点。J.M.Tarascom等人报导了以Li2CO3或LiNO3和电解MnO2为原料合成LiMn2O4[J.Electrochem.Soc.141，No.6，June1994，1421-1431]，该方法需在800℃下分两次分别合成24h和48h，然后再以5～10℃/h的速度冷却，所得产物的工作电位为4.2～3.0V。文献[J.PowerSource，41(1993)305～314]报导的方法合成时间则更长。文献[J.Electrochem.Soc.Vol 138 No.10(1991).2859-2868]报导了以Li2CO3、MnO2为原料，在600～1100℃间不同温度下合成LiMn2O4的方法，所得产物的比容量为90～105mAh/g。其它文献公开的方法，或者是合成温度高，时间长，或者是所得产物的性能指标不理想。
发明内容
本发明的目的在于提供一种制备锂离子电池正极材料LiMn2O4的新方法，该方法应在保证产品质量的稳定性、可靠性和均匀性的前提下，从国内廉价原材料出发，具有生产成本低，工艺简单，适合于规模化生产的特点。
为实现上述目的所采用的技术措施是：
制备LiMn2O4材料是以二氧化锰(MnO2)、碳酸锰(MnCO3)、硝酸锰(Mn(NO3)2)或醋酸锰(Mn(CH3COO)2)和氢氧化锂(LiOH)、碳酸锂(Li2CO3)或硝酸锂(LiNO3)作原料，合成基本反应为：
具体制备方法如下：以MnO2、MnCO3、Mn(NO3)2、或Mn(CH3COO)2和LiOH、Li2CO3或LiNO3为原料，按锂与锰的摩尔比为0.45～0.5的比例混合，经球磨均匀后压成块状，在600～800℃烧结36小时，冷却后取出，粉碎球磨，用300目分样筛过筛即得产品，后收集产品，密封储存备用。
所得的LiMn2O4具有尖晶石层状结构，经测试，该材料的电性能达到120mAh/g比容量，工作电位在4.15～3.70伏(相对于锂参比电极)，与价格昂贵的LiCoO2材料相当，而其成本仅为LiCoO2材料的4.5％左右，因此，LiMn2O4是先进的锂离子电池首选的正极材料。
与已有技术相比，采用本发明的技术措施所取得的有益效果：
本发明的锂离子电池正极材料LiMn2O4的制备方法具有以下几个显著特点：
1)制备的LiMn2O4材料性能优良，在0.25C放电率下，可以达到120mAh/g的比容量，放电电位在4.15至3.70伏(相对锂参比电极)。
2)制备的材料价格低廉，如以MnO2和LiOH作原料，制造1Kg LiMn2O4仅需原材料费24.70元/Kg。
3)工艺简单，合成时间短，易于掌握，容易实现工业化规模生产。
4)清洁无污染，不含任何有害元素。
附图说明
图1是用本发明方法制得的LiMn2O4材料制成电极在0.25C放电率下的放电曲线。
具体实施方式
下面结合实施例对本发明作进一步的说明：
实施例：
准确称取MnO2 348g、LiOH·H2O 84g，在球磨机中球磨混合15～20分钟，将混合料置于模具中在油压机上压成块状，放置在高温炉中加热，在600℃至800℃分段烧结共36小时，冷却后取出粉碎球磨，过300目分样筛，即成锂离子电池用LiMn2O4正极材料。收集密封备用。
Claims (2)
1.一种高性能锂离子电池正极材料LiMn2O4的制备方法，其特征在于该方法是以MnO2、MnCO3、Mn(NO3)2、或Mn(CH3COO)2和LiOH、Li2CO3或LiNO3为原料，按锂与锰的摩尔比为0.45～0.5的比例混合，经球磨均匀后压成块状，在600～800℃烧结36小时，冷却后取出，粉碎球磨，用300目分样筛过筛即得产品。
2.按权利要求1所述的制各方法，其特征在于所述的LiMn2O4具有尖晶石层状结构，用锂电极作参比时的工作电位在4.15到3.70伏，在0.25C放电率下的比容量为120mAh/g。
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|---|---|---|---|
| CN97109010A CN1095599C (zh) | 1997-01-17 | 1997-01-17 | 高性能锂离子电池正极材料LiMn2O4的制备方法 |
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| CN97109010A CN1095599C (zh) | 1997-01-17 | 1997-01-17 | 高性能锂离子电池正极材料LiMn2O4的制备方法 |
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| Publication Number | Publication Date |
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| CN1166698A CN1166698A (zh) | 1997-12-03 |
| CN1095599C true CN1095599C (zh) | 2002-12-04 |
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| CN103594697B (zh) * | 2013-11-11 | 2015-12-30 | 甘肃大象能源科技有限公司 | 一种由高锰酸钾锰废渣制备锰酸锂正极材料的方法 |
| CN110137457A (zh) * | 2019-05-08 | 2019-08-16 | 贵州丕丕丕电子科技有限公司 | 一种包覆型锰酸锂正极材料、制备方法及锂离子电池 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02865A (ja) * | 1987-12-04 | 1990-01-05 | Matsushita Electric Ind Co Ltd | 感光材料およびそれを用いたパターン形成方法 |
| JPH0254865A (ja) * | 1988-08-20 | 1990-02-23 | Japan Storage Battery Co Ltd | 非水電解液二次電池およびそれに用いる正極活物質の製造方法 |
| US4980080A (en) * | 1988-06-09 | 1990-12-25 | Societe Anonyme Dite: Saft | Process of making a cathode material for a secondary battery including a lithium anode and application of said material |
-
1997
- 1997-01-17 CN CN97109010A patent/CN1095599C/zh not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02865A (ja) * | 1987-12-04 | 1990-01-05 | Matsushita Electric Ind Co Ltd | 感光材料およびそれを用いたパターン形成方法 |
| US4980080A (en) * | 1988-06-09 | 1990-12-25 | Societe Anonyme Dite: Saft | Process of making a cathode material for a secondary battery including a lithium anode and application of said material |
| JPH0254865A (ja) * | 1988-08-20 | 1990-02-23 | Japan Storage Battery Co Ltd | 非水電解液二次電池およびそれに用いる正極活物質の製造方法 |
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| Publication number | Publication date |
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| CN1166698A (zh) | 1997-12-03 |
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