CN1643714A - 正极活性物质和使用该物质的非水电解质电池 - Google Patents
正极活性物质和使用该物质的非水电解质电池 Download PDFInfo
- Publication number
- CN1643714A CN1643714A CNA038069350A CN03806935A CN1643714A CN 1643714 A CN1643714 A CN 1643714A CN A038069350 A CNA038069350 A CN A038069350A CN 03806935 A CN03806935 A CN 03806935A CN 1643714 A CN1643714 A CN 1643714A
- Authority
- CN
- China
- Prior art keywords
- lithium
- battery
- active material
- manganese
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 70
- 239000013543 active substance Substances 0.000 title 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 142
- 239000011572 manganese Substances 0.000 claims abstract description 124
- 239000007774 positive electrode material Substances 0.000 claims abstract description 78
- 239000002131 composite material Substances 0.000 claims abstract description 59
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 45
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 29
- 239000010941 cobalt Substances 0.000 claims abstract description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910015645 LiMn Inorganic materials 0.000 claims description 40
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 25
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- 239000011029 spinel Substances 0.000 claims description 18
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 11
- 229910021314 NaFeO 2 Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 79
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 34
- 229910052748 manganese Inorganic materials 0.000 abstract description 30
- 230000003247 decreasing effect Effects 0.000 abstract 1
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- 239000011149 active material Substances 0.000 description 74
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- 238000002156 mixing Methods 0.000 description 13
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- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
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- 229910018651 Mn—Ni Inorganic materials 0.000 description 9
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- 229910052799 carbon Inorganic materials 0.000 description 9
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
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- 239000012535 impurity Substances 0.000 description 9
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910017709 Ni Co Inorganic materials 0.000 description 8
- 229910003267 Ni-Co Inorganic materials 0.000 description 8
- 229910003262 Ni‐Co Inorganic materials 0.000 description 8
- 229940044175 cobalt sulfate Drugs 0.000 description 8
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000005755 formation reaction Methods 0.000 description 8
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- 239000000047 product Substances 0.000 description 8
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- 238000003756 stirring Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 229910012820 LiCoO Inorganic materials 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 229910000765 intermetallic Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000013049 sediment Substances 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 229910018539 Ni—Mn—Co Inorganic materials 0.000 description 6
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- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920001959 vinylidene polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910000634 wood's metal Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
Description
电池 | 组成 | |b-c| | d | 初始放电容量(mAh/g) | 高速放电性能值(%) | 高温充电容量增长率(%) |
实施例1 | LiMn0.005Ni0.005Co0.99O2 | 0 | 0.99 | 153 | 92 | 1.9 |
实施例2 | LiMn0.01Ni0.01Co0.98O2 | 0 | 0.98 | 148 | 92 | 2.0 |
实施例3 | LiMn0.025Ni0.025Co0.95O2 | 0 | 0.95 | 149 | 95 | 1.6 |
实施例4 | LiMn0.05Ni0.05Co0.90O2 | 0 | 0.9 | 150 | 95 | 1.7 |
实施例5 | LiMn0.0835Ni0.0835Co0.833O2 | 0 | 0.833 | 152 | 92 | 2.5 |
比较例1 | LiCoO2 | - | 1 | 156 | 83 | 3.7 |
实施例6 | LiMn0.165Ni0.165Co0.67O2 | 0 | 0.67 | 151 | 88 | 5.0 |
实施例7 | LiMn0.04Ni0.01Co0.95O2 | 0.03 | 0.95 | 146 | 92 | 3.0 |
实施例8 | LiMn0.01Ni0.04Co0.95O2 | 0.03 | 0.95 | 151 | 94 | 4.0 |
比较例2 | LiMn0.25Ni0.25Co0.50O2 | 0 | 0.5 | 149 | 87 | 5.3 |
比较例3 | LiMn0.13Ni0.07Co0.80O2 | 0.06 | 0.8 | 148 | 92 | 3.0 |
比较例4 | LiMn0.07Ni0.13Co0.80O2 | 0.06 | 0.8 | 149 | 90 | 2.4 |
活性物质的名称 | 组成 | |b-c| | d | 初始放电容量(mAh/g) | 高速放电性能值(%) | 高温充电容量增长率(%) |
B01-a | LiMn0.005Ni0.005Co0.99O2 | 0 | 0.99 | 153 | 92 | 1.9 |
B02-a | LiMn0.011Ni0.01Co0.98O2 | 0 | 0.98 | 148 | 92 | 2.0 |
B03-a | LiMn0.025Ni0.025Co0.95O2 | 0 | 0.95 | 149 | 95 | 1.6 |
B03-b | LiMn0.025Ni0.025Co0.95O2 | 0 | 0.95 | 149 | 95 | 1.6 |
B04-a | LiMn0.05Ni0.05Co0.90O2 | 0 | 0.9 | 150 | 95 | 1.7 |
B05-a | LiMn0.0835Ni0.0835Co0.833O2 | 0 | 0.833 | 152 | 92 | 2.5 |
B-Co | LiCoO2 | - | 1 | 156 | 83 | 3.7 |
B11-a | LiMn0.165Ni01.65Co0.67O2 | 0 | 0.67 | 151 | 88 | 5.0 |
B12-a | LiMn0.04Ni0.01Co0.95O2 | 0.03 | 0.95 | 146 | 92 | 3.0 |
B13-b | LiMn0.01Ni0.04Co0.95O2 | 0.03 | 0.95 | 151 | 94 | 4.0 |
B14-b | LiM0.42Ni0.42Co0.16O2 | 0 | 0.16 | 158 | 83 | 9.1 |
B15-b | LiMn0.25Ni0.25Co0.50O2 | 0 | 0.5 | 155 | 86 | 7.3 |
A | Li1.08Mn1.92O4 | - | - | 94 | 91 | 2.3 |
电池 | 活性物质B的名称 | B的比例(重量%) | 初始放电容量(mAh/g) | 高速放电性能值(%) | 自放电率(%) | 容量恢复率(%) | 针刺测试 |
比较例5 | - | 0 | 94 | 91.0 | 15.4 | 90.9 | ○ |
实施例9 | B-03b | 5 | 97 | 91.1 | 15.3 | 91.0 | ○ |
实施例10 | B-03b | 10 | 100 | 91.4 | 14.8 | 91.6 | ○ |
实施例11 | B-03b | 30 | 114 | 91.8 | 12.0 | 94.2 | ○ |
实施例12 | B-03b | 50 | 119 | 92.2 | 10.9 | 96.0 | ○ |
实施例13 | B-03b | 70 | 133 | 92.6 | 10.2 | 97.1 | ○ |
实施例14 | B-03b | 90 | 144 | 93.8 | 9.6 | 97.9 | ○ |
实施例15 | B-03b | 95 | 146 | 94.8 | 9.5 | 98.0 | ○ |
参考例1 | B-03b | 100 | 149 | 95.0 | 9.5 | 98.0 | × |
实施例16 | B-05b | 50 | 120 | 91.1 | 10.7 | 96.2 | ○ |
比较例6 | B-15b | 50 | 117 | 87.3 | 9.3 | 96.7 | ○ |
Claims (6)
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JP2002088229 | 2002-03-27 | ||
JP88229/2002 | 2002-03-27 | ||
JP2002137870 | 2002-05-14 | ||
JP137870/2002 | 2002-05-14 | ||
PCT/JP2003/003691 WO2003081698A1 (fr) | 2002-03-27 | 2003-03-26 | Substance active pour electrode positive et batterie a electrolyte non aqueuse renfermant ladite substance |
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US (1) | US7691535B2 (zh) |
EP (1) | EP1469539B1 (zh) |
JP (1) | JP4541709B2 (zh) |
CN (1) | CN1315212C (zh) |
AU (1) | AU2003221171A1 (zh) |
WO (1) | WO2003081698A1 (zh) |
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2003
- 2003-03-26 CN CNB038069350A patent/CN1315212C/zh not_active Expired - Fee Related
- 2003-03-26 WO PCT/JP2003/003691 patent/WO2003081698A1/ja active Application Filing
- 2003-03-26 US US10/500,819 patent/US7691535B2/en active Active
- 2003-03-26 AU AU2003221171A patent/AU2003221171A1/en not_active Abandoned
- 2003-03-26 EP EP03712972A patent/EP1469539B1/en not_active Expired - Lifetime
- 2003-03-26 JP JP2003579300A patent/JP4541709B2/ja not_active Expired - Fee Related
Cited By (10)
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TWI453980B (zh) * | 2007-09-28 | 2014-09-21 | 3M Innovative Properties Co | 燒結陰極組合物 |
CN101872863A (zh) * | 2010-07-13 | 2010-10-27 | 深圳邦凯新能源股份有限公司 | 一次用圆柱聚合物锂离子电池及其制造方法 |
CN102738457A (zh) * | 2011-04-07 | 2012-10-17 | 锂科科技股份有限公司 | 锂离子电池正极金属氧化物材料及锂离子电池 |
CN102738457B (zh) * | 2011-04-07 | 2014-10-08 | 锂科科技股份有限公司 | 锂离子电池正极金属氧化物材料及锂离子电池 |
CN103872310A (zh) * | 2012-12-12 | 2014-06-18 | 三星Sdi株式会社 | 可再充电锂电池用正极活性物质、正极和可再充电锂电池 |
CN103872310B (zh) * | 2012-12-12 | 2018-04-06 | 三星Sdi株式会社 | 可再充电锂电池用正极活性物质、正极和可再充电锂电池 |
CN103847422A (zh) * | 2013-01-22 | 2014-06-11 | 洛阳甲天下牡丹园艺有限公司 | 一种牡丹、芍药国画式艺术压花画及其制作方法 |
CN105594023A (zh) * | 2013-03-15 | 2016-05-18 | 纳诺万材料公司 | 用于电池应用的层状锂混合金属氧化物的微细和超微细粉末以及纳米粉末的工业生产的配位前驱体配制方法 |
CN104078666A (zh) * | 2013-03-28 | 2014-10-01 | 三星Sdi株式会社 | 制备正极活性物质的方法、可再充电锂电池和电子装置 |
CN104078666B (zh) * | 2013-03-28 | 2018-05-22 | 三星Sdi株式会社 | 制备正极活性物质的方法、可再充电锂电池和电子装置 |
Also Published As
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EP1469539A1 (en) | 2004-10-20 |
CN1315212C (zh) | 2007-05-09 |
JPWO2003081698A1 (ja) | 2005-07-28 |
WO2003081698A1 (fr) | 2003-10-02 |
US20050019659A1 (en) | 2005-01-27 |
EP1469539B1 (en) | 2012-08-01 |
US7691535B2 (en) | 2010-04-06 |
JP4541709B2 (ja) | 2010-09-08 |
AU2003221171A1 (en) | 2003-10-08 |
EP1469539A4 (en) | 2007-08-29 |
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