CN1773749A - Method for producing Sc (III) doped spinel type lithium manganate cell positive electrode material - Google Patents

Method for producing Sc (III) doped spinel type lithium manganate cell positive electrode material Download PDF

Info

Publication number
CN1773749A
CN1773749A CNA2004100657236A CN200410065723A CN1773749A CN 1773749 A CN1773749 A CN 1773749A CN A2004100657236 A CNA2004100657236 A CN A2004100657236A CN 200410065723 A CN200410065723 A CN 200410065723A CN 1773749 A CN1773749 A CN 1773749A
Authority
CN
China
Prior art keywords
positive electrode
calcination
hour
product
lisc
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
Application number
CNA2004100657236A
Other languages
Chinese (zh)
Other versions
CN100379060C (en
Inventor
周复
赵雪梅
郑化桂
沈涛
季明荣
张祖德
唐琛明
王新威
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology of China USTC
Original Assignee
University of Science and Technology of China USTC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Science and Technology of China USTC filed Critical University of Science and Technology of China USTC
Priority to CNB2004100657236A priority Critical patent/CN100379060C/en
Publication of CN1773749A publication Critical patent/CN1773749A/en
Application granted granted Critical
Publication of CN100379060C publication Critical patent/CN100379060C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • 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

Landscapes

  • Battery Electrode And Active Subsutance (AREA)

Abstract

A method for preparing Sc (III) doped positive electrode material of lithium manganese cell in spine type includes using LiOH.H2O, MnO2 as initial material, mixing Sc2O3 in said material as per LiSc4Mn2 - y substance ratio of x = 0.01-0.2, firing for 3 - 6hr. at 450 - 500 deg.c after grinding, grinding again then firing for 3 - 6hr. at 500 - 550 deg.c, firing for 12 - 24hr. at 600 - 800 deg.c after grinding; or adding mixed dispersing agent formed by alcohol and distilled water into initial material as per amount of adding 100 - 200ml formed agent into each mole of initial material when Sc2O3 is mixed in and then firing it for 12 - 24hr. at 600 - 800 deg.c after grinding.

Description

The preparation method of the spinel type lithium manganate cell positive electrode material that a kind of Sc (III) mixes
Technical field:
The invention belongs to the technology of preparing of cell positive material, particularly the preparation method of lithium cell anode material lithium manganate.
Background technology:
Introduce lithium manganate having spinel structure LiMn according to " new material industry " first phase 23-24 in 2004 page or leaf 2O 4As the positive electrode of lithium ion battery, with respect to LiCoO 2, LiNiO 2Deng positive electrode, because its environmental pollution is little, raw material sources are extensive, and are cheap, discharge and recharge the high characteristics of coefficient of safety, and prospect has a very wide range of applications.Introduce according to " Chinese manganese industry " the 21st volume first phase 14-18 page or leaf, main chemical preparation process has solid phase segmented high-temperature calcination method at present, Page Buddhist nun (Pechini) method, and sol-gel process etc., the energy consumption that these preparation methods have is big, the calcination temperature height, the time is long; The process complexity that has is operated complicated; And the cycle performance of product is poor.
" Chinese manganese industry " the 21st volume first phase 14-18 page or leaf report, the manganate cathode material for lithium of metering type is in the process of charge and discharge cycles, because ginger-Taylor's (Jahn-Teller) effect of Mn (III) and the influences such as dissolving of manganese, cause the distortion that is distorted of the three-dimensional cubic major path structure of spinel-type, structure is extremely unstable, capacity attenuation is rapid, and cyclicity is very poor.For improving the cyclicity of spinel-type positive electrode, the metal ion of doping divalence or trivalent in spinel structure, thus the content of minimizing Mn (III) begins to cause people's attention, but in the present doping research, the cycle performance of material is not significantly improved.
Holland " power material " magazine (Journal of Power Sources, 102:21-28,2001) reported the research work of doping Co in the spinel-type positive electrode, but high-temperature calcination overlong time in this technological process, energy consumption is big, is unfavorable for large-scale popularization.
" power material " magazine (Journal of Power Sources, 96:376-384,2001) reported the research work of doped with Al in the spinel-type positive electrode, this method production procedure energy consumption is less, but the positive electrode cycle performance after mixing is still undesirable, and capacity attenuation is very fast.
China's " Journal of Inorganic Materials " 2002 the 17th volumes the 5th phase 999-1003 page or leaf has been reported the research work of doping Co in the spinel-type positive electrode, this technological process has adopted solution to be combined to technology, production cycle is long, and experimental procedure is loaded down with trivial details, and the performance of product is very not outstanding.
For improving the practicality of spinel-type positive electrode, need to seek a kind of suitable production technology prescription and production procedure, to improve the electrochemistry cyclicity and the structural stability of spinel-type positive electrode.
Summary of the invention:
The present invention proposes the preparation method of the spinel type lithium manganate cell positive electrode material of a kind of Sc (III) doping, to improve the electrochemistry cyclicity and the structural stability of spinel-type positive electrode.
The preparation method of the spinel type lithium manganate cell positive electrode material that Sc of the present invention (III) mixes adopts the solid phase high-temperature calcination, and initial material is with LiOHH 2O is as lithium source, MnO 2As the manganese source, it is characterized in that: according to LiSc xMn 2-xO 4The ratio of middle amount is got x=0.01-0.2, is mixing Sc in initial material 2O 3, behind the mixed grinding, 450-500 ℃ calcination 3-6 hour, obtain intermediate product; After the grinding, again in 500-550 ℃ of calcination 3-6 hour; Grind the back again in 600-800 ℃ of calcination 12-24 hour, promptly get end product.
If with Sc 2O 3Mix in the process of initial material, by every mole of initial material add the 100-200 milliliter by ethanol: the distilled water volume ratio is the mixed dispersant that 2:3 forms, and in 600-800 ℃ of calcination 12-24 hour, promptly gets end product behind the mixed grinding.
Compared with prior art, the inventive method preparation process is simple, and reaction time is short, and prospects for commercial application is good; Behind the doping Sc (III), material has still kept intact spinel-type three-dimensional cubic major path structure; In the doping scope of x=0.01-0.2, the decline that reduces the first capacity that causes owing to the content of Mn (III) is also less, and first discharge capacity remains on more than the 110mAh/g; Behind the doping Sc (III), the cycle performance of material significantly improves, with LiSc xMn 2-xO 4, x=0.01-0.2, as the battery of positive electrode preparation, after interval interior 60 charge and discharge cycles of 3-4.5V, the capacity attenuation rate only is 2-4%; After 60 circulations were finished, XRD tested demonstration, LiSc xMn 2-xO 4(x=0.01-0.2) the spinel-type three-dimensional cubic major path structure that still remains intact of positive electrode.Adopt this method, the chemical property of lithium manganate having spinel structure positive electrode has obtained promoting greatly, thereby is spinel-type LiMn 2O 4Application in lithium ion battery industry provides an effective way.
Embodiment:
Below be embodiments of the invention:
Embodiment 1:LiSc 0.01Mn 1.99O 4Preparation
According to stoichiometric proportion, take by weighing LiOHH 2The O2.1 gram, MnO 28.65 gram, Sc 2O 30.0345 gram, mixed grinding placed muffle furnace after 1 hour, was warming up to 450 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 5 hours naturally cools to room temperature; Intermediate product take out to grind after 0.5 hour, was warming up to 520 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 5 hours naturally cools to room temperature; Intermediate product take out to grind after 0.5 hour, was warming up to 800 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 12 hours naturally cools to room temperature, and product grinds after 15 minutes and collects, and obtains final product.
Adopting X-ray diffraction, scanning electron microscopy that the thing of product is reached pattern mutually analyzes, X-ray diffraction peak before and after the product circulation meets the spinel structure of cube phase fully, stereoscan photograph shows that the particle diameter of product presents the octahedral build profile of rule between 1-4um.
With the LiSc for preparing 0.01Mn 1.99O 4Be positive electrode, lithium metal is a negative pole, makes battery, measures its electrochemical properties in the 3-4.5V scope, and test result shows: LiSc 0.01Mn 1.99O 4The first discharge capacity of material is 125mAh/g, and 60 times circulation back capacity still remains on 120mAh/g, and the capacity attenuation rate is 4%, shows that the cyclicity of the electrode material after the doping is significantly improved.
Embodiment 2:LiSc 0.02Mn 1.98O 4Preparation
According to stoichiometric proportion, take by weighing LiOHH 2The O2.1 gram, MnO 28.6 gram, Sc 2O 30.069 gram, mixed grinding placed muffle furnace after 1 hour, was warming up to 460 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 3 hours naturally cools to room temperature; Intermediate product take out to grind after 0.5 hour, was warming up to 550 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 3 hours naturally cools to room temperature; Intermediate product take out to grind after 0.5 hour, was warming up to 600 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 18 hours naturally cools to room temperature, and product grinds after 15 minutes and collects, and obtains final product.
Adopting X-ray diffraction, scanning electron microscopy that the thing of product is reached pattern mutually analyzes, X-ray diffraction peak before and after the product circulation meets the spinel structure of cube phase fully, stereoscan photograph shows that the particle diameter of product presents the octahedral build profile of rule between 1-4um.
With the LiSc for preparing 0.02Mn 1.98O 4Be positive electrode, lithium metal is a negative pole, makes battery, measures its electrochemical properties in the 3-4.5V scope, and test result shows: LiSc 0.02Mn 1.98O 4The first discharge capacity of material is 100mAh/g, and 60 times circulation back capacity still remains on 98mAh/g, and the capacity attenuation rate is 2%, shows the cyclicity that adopts this kind doping method can effectively improve material really.
Embodiment 3:LiSc 0.06Mn 1.94O 4Preparation
According to stoichiometric proportion, take by weighing LiOHH 2The O2.1 gram, MnO 28.44 gram, Sc 2O 30.21 gram, mixed grinding placed muffle furnace after 1 hour, was warming up to 480 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 5 hours naturally cools to room temperature; Intermediate product take out to grind after 0.5 hour, was warming up to 550 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 5 hours naturally cools to room temperature; Intermediate product take out to grind after 0.5 hour, was warming up to 700 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 24 hours naturally cools to room temperature, and product grinds after 15 minutes and collects, and obtains final product.
X-ray diffraction result before and after the product circulation shows that products therefrom is the spinel structure of cube phase, and stereoscan photograph shows that the particle diameter of product presents the octahedral build profile of rule between 1-4um.
With the LiSc for preparing 0.06Mn 1.94O 4Be positive electrode, lithium metal is a negative pole, makes battery, measures its electrochemical properties in the 3-4.5V scope, and test result shows: LiSc 0.06Mn 1.94O 4The first discharge capacity of material is 135mAh/g, and 60 times circulation back capacity still remains on 132mAh/g, and the capacity attenuation rate is 2%, and than unadulterated material, cyclicity is greatly improved.
Embodiment 4:LiSc 0.1Mn 1.9O 4Preparation
According to stoichiometric proportion, take by weighing LiOHH 2The O2.1 gram, MnO 28.27 gram, Sc 2O 30.345 gram, mixed grinding placed muffle furnace after 1 hour, was warming up to 470 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 4 hours naturally cools to room temperature; Intermediate product take out to grind after 0.5 hour, was warming up to 530 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 4 hours naturally cools to room temperature; Intermediate product take out to grind after 0.5 hour, was warming up to 600 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 24 hours naturally cools to room temperature, and product grinds after 15 minutes and collects, and obtains final product.
Adopting X-ray diffraction, scanning electron microscopy that the thing of product is reached pattern mutually analyzes, X-ray diffraction peak before and after the product circulation shows that material belongs to the spinel structure of cube phase, stereoscan photograph shows that the particle diameter of product presents the octahedral build profile of rule between 1-4um.
With the LiSc for preparing 0.1Mn 1.9O 4Be positive electrode, lithium metal is a negative pole, makes battery, measures its electrochemical properties in the 3-4.5V scope, and test result shows: LiSc 0.1Mn 1.9O 4The first discharge capacity of material is 128mAh/g, and 60 times circulation back capacity still remains on 123mAh/g, and the capacity attenuation rate is 4%, has shown the good cyclicity of the back material that mixes.
Embodiment 5:LiSc 0.2Mn 1.8O 4Preparation
According to stoichiometric proportion, take by weighing LiOHH 2The O2.1 gram, MnO 27.83 gram, Sc 2O 30.69 gram, mixed grinding placed muffle furnace after 1 hour, was warming up to 490 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 3 hours naturally cools to room temperature; Intermediate product take out to grind after 0.5 hour, was warming up to 520 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 3 hours naturally cools to room temperature; Intermediate product take out to grind after 0.5 hour, was warming up to 700 ℃ with the speed of 5 ℃/min, kept temperature, and calcination 12 hours naturally cools to room temperature, and product grinds after 15 minutes and collects, and obtains final product.
Adopting X-ray diffraction, scanning electron microscopy that the thing of product is reached pattern mutually analyzes, X-ray diffraction peak before and after the product circulation all meets the spinel structure of cube phase, stereoscan photograph shows that the particle diameter of product presents the octahedral build profile of rule between 1-4um.
With the LiSc for preparing 0.2Mn 1.8O 4Be positive electrode, lithium metal is a negative pole, makes battery, measures its electrochemical properties in the 3-4.5V scope, and test result shows: LiSc 0.2Mn 1.8O 4The first discharge capacity of material is 116mAh/g, and 60 times circulation back capacity still remains on 112mAh/g, and the capacity attenuation rate is 3.4%, and with respect to unadulterated spinelle sample, its chemical property has had significant raising.
Embodiment 6:LiSc 0.08Mn 1.92O 4Preparation
According to stoichiometric proportion, take by weighing LiOHH 2The O2.1 gram, MnO 28.352 gram, Sc 2O 30.276 gram adds 2: 3 ethanol of volume ratio: 20 milliliters of distilled water mixed dispersants, mixed grinding is after 1 hour, 80 ℃ of oven dry place muffle furnace, are warming up to 600 ℃ with the speed of 5 ℃/min, calcination 12 hours naturally cools to room temperature, can obtain final product.
Adopting X-ray diffraction, scanning electron microscopy that the thing of product is reached pattern mutually analyzes, X-ray diffraction peak before and after the product circulation shows that material belongs to the spinel structure of cube phase, stereoscan photograph shows, the particle diameter of product presents the octahedral build profile of rule between 0.5-1um.
With the LiSc for preparing 0.08Mn 1.92O 4Be positive electrode, lithium metal is a negative pole, makes battery, measures its electrochemical properties in the 3-4.5V scope, and test result shows: LiSc 0.08Mn 1.92O 4First discharge capacity be 136mAh/g, 60 times circulation back capacity still remains on 132mAh/g, the capacity attenuation rate is 3%, cycle performance significantly promotes.
Embodiment 7:LiSc 0.15Mn 1.85O 4Preparation
According to stoichiometric proportion, take by weighing LiOHH 2The O2.1 gram, MnO 28.0475 gram, Sc 2O 30.5175 gram adds 2: 3 ethanol of volume ratio: 15 milliliters of distilled water mixed dispersants, mixed grinding is after 1 hour, 80 ℃ of oven dry place muffle furnace, are warming up to 700 ℃ with the speed of 5 ℃/min, calcination 18 hours naturally cools to room temperature, can obtain final product.
Adopting X-ray diffraction, scanning electron microscopy that the thing of product is reached pattern mutually analyzes, X-ray diffraction peak before and after the product circulation shows that material belongs to the spinel structure of cube phase, stereoscan photograph shows, the particle diameter of product presents the octahedral build profile of rule between 0.5-1.5um.
With the LiSc for preparing 0.15Mn 1.85O 4Be positive electrode, lithium metal is a negative pole, makes battery, measures its electrochemical properties in the 3-4.5V scope, and test result shows: LiSc 0.15Mn 1.85O 4The first discharge capacity of material is 128mAh/g, and 60 times circulation back capacity still remains on 125mAh/g, and the capacity attenuation rate is 2.3%, and cycle performance significantly improves.
Embodiment 8:LiSc 0.2Mn 1.8O 4Preparation
According to stoichiometric proportion, take by weighing LiOHH 2The O2.1 gram, MnO 27.83 gram, Sc 2O 30.69 gram adds 2: 3 ethanol of volume ratio: 30 milliliters of distilled water mixed dispersants, mixed grinding be after 1 hour, 80 ℃ of oven dry, place muffle furnace, be warming up to 800 ℃, keep temperature with the speed of 5 ℃/min, calcination 24 hours naturally cools to room temperature, can obtain final product.
Adopting X-ray diffraction, scanning electron microscopy that the thing of product is reached pattern mutually analyzes, X-ray diffraction peak before and after the product circulation shows that material belongs to the spinel structure of cube phase, stereoscan photograph shows, the particle diameter of product presents the octahedral build profile of rule between 0.5-2um.
With the LiSc for preparing 0.2Mn 1.8O 4Be positive electrode, lithium metal is a negative pole, makes battery, measures its electrochemical properties in the 3-4.5V scope, and test result shows: LiSc 0.2Mn 1.8O 4The first discharge capacity of material is 120mAh/g, and 60 times circulation back capacity still remains on 117mAh/g, and the capacity attenuation rate is 2.5%, and with respect to unadulterated spinel type materials, cycle performance has obtained significant lifting.

Claims (2)

1, the preparation method of the spinel type lithium manganate cell positive electrode material of a kind of Sc (III) doping adopts the solid phase high-temperature calcination, and initial material is with LiOHH 2O is as lithium source, MnO 2As the manganese source, it is characterized in that: according to LiSc xMn 2-xO 4The ratio of middle amount is got x=0.01-0.2, is mixing Sc in initial material 2O 3, behind the mixed grinding, 450-500 ℃ calcination 3-6 hour, obtain intermediate product; After the grinding, again in 500-550 ℃ of calcination 3-6 hour; Grind the back again in 600-800 ℃ of calcination 12-24 hour, promptly get end product.
2, the preparation method of lithium manganate cell positive electrode material according to claim 1 is characterised in that with Sc 2O 3Mix in the process of initial material, by every mole of initial material add the 100-200 milliliter by ethanol: the distilled water volume ratio is 2: 3 mixed dispersants of forming, and in 600-800 ℃ of calcination 12-24 hour, promptly gets end product behind the mixed grinding.
CNB2004100657236A 2004-11-11 2004-11-11 Method for producing Sc (III) doped spinel type lithium manganate cell positive electrode material Expired - Fee Related CN100379060C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2004100657236A CN100379060C (en) 2004-11-11 2004-11-11 Method for producing Sc (III) doped spinel type lithium manganate cell positive electrode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2004100657236A CN100379060C (en) 2004-11-11 2004-11-11 Method for producing Sc (III) doped spinel type lithium manganate cell positive electrode material

Publications (2)

Publication Number Publication Date
CN1773749A true CN1773749A (en) 2006-05-17
CN100379060C CN100379060C (en) 2008-04-02

Family

ID=36760584

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2004100657236A Expired - Fee Related CN100379060C (en) 2004-11-11 2004-11-11 Method for producing Sc (III) doped spinel type lithium manganate cell positive electrode material

Country Status (1)

Country Link
CN (1) CN100379060C (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102916196A (en) * 2012-10-30 2013-02-06 桑德环境资源股份有限公司 Method for preparing lithium-manganate battery cathode material admixed with scandium by ion implanter
CN103606669A (en) * 2013-11-28 2014-02-26 福建师范大学 Preparation method of trivalent scandium or chromium-doped spinel-type lithium-rich lithium manganate cathode material
CN104409722A (en) * 2014-12-17 2015-03-11 湖南杉杉新能源有限公司 Method for improving performance of lithium manganate cathode material
CN109950534A (en) * 2019-03-15 2019-06-28 北京理工大学 A kind of nickelic tertiary cathode material of Sc doping vario-property

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3975614B2 (en) * 1999-06-11 2007-09-12 三菱マテリアル株式会社 Positive electrode active material for lithium secondary battery, method for producing the same, and lithium secondary battery using the same
US6350543B2 (en) * 1999-12-29 2002-02-26 Kimberly-Clark Worldwide, Inc. Manganese-rich quaternary metal oxide materials as cathodes for lithium-ion and lithium-ion polymer batteries
JP2002042812A (en) * 2000-07-27 2002-02-08 Yuasa Corp Positive electrode active material for lithium secondary battery and lithium secondary battery using the same
JP3972577B2 (en) * 2000-12-04 2007-09-05 株式会社ジーエス・ユアサコーポレーション Lithium secondary battery

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102916196A (en) * 2012-10-30 2013-02-06 桑德环境资源股份有限公司 Method for preparing lithium-manganate battery cathode material admixed with scandium by ion implanter
CN103606669A (en) * 2013-11-28 2014-02-26 福建师范大学 Preparation method of trivalent scandium or chromium-doped spinel-type lithium-rich lithium manganate cathode material
CN103606669B (en) * 2013-11-28 2016-01-20 福建师范大学 Mix the preparation method of the spinel lithium-rich lithium manganate cathode material of trivalent scandium or chromium
CN104409722A (en) * 2014-12-17 2015-03-11 湖南杉杉新能源有限公司 Method for improving performance of lithium manganate cathode material
CN109950534A (en) * 2019-03-15 2019-06-28 北京理工大学 A kind of nickelic tertiary cathode material of Sc doping vario-property

Also Published As

Publication number Publication date
CN100379060C (en) 2008-04-02

Similar Documents

Publication Publication Date Title
CN102044671B (en) Spinel type lithium manganate electrode material and preparation method thereof
CN112599783B (en) Selenium-doped lithium-rich manganese-based positive electrode material and preparation method and application thereof
CN113113589B (en) Method for improving superlattice structure of sodium ion layered positive electrode material
CN102088085A (en) Lithium ion battery positive material and preparation method thereof
CN105789581A (en) Production method for high-capacity long-cycle lithium-rich type-622 ternary positive electrode material
CN1719639A (en) Method ofr prpearing high-lithium ion content laminated lithium manganate anode material
CN105789607A (en) Preparation method of lithium titanate anode material doped with rare earth
CN113845152A (en) Lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery
CN113078316B (en) Lithium molybdate-coated lithium-rich manganese-based positive electrode material and preparation method and application thereof
CN114975984A (en) Preparation method of porous core-shell structure nickel-rich cathode material
CN111509224B (en) Linked modified lithium-rich manganese-based cathode material and preparation method thereof
CN101179125B (en) Method of producing silicon doped LiMn2O4 lithium ion battery anode material
CN114671468B (en) Preparation method and application of polyanion and Prussian blue composite positive electrode material
CN103594704B (en) The preparation method of the spinel lithium-rich lithium manganate cathode material of doping titanic ion
CN100379060C (en) Method for producing Sc (III) doped spinel type lithium manganate cell positive electrode material
CN1872702A (en) Method for preparing spinel type lithium manganate in use for material of positive pole in lithium ion battery
CN1234177C (en) Method for improving high-temperature performance of lithium ion battery positive material LiMn2O4
CN1803592A (en) Method for preparing lithium enriched lithium ion phosphate powder
CN117682568A (en) Spherical K 0.44 Mn 0.78 Ni 0.22 O 1.8 F 0.2 Preparation method and application of positive electrode material
CN103594702B (en) The standby method of mixing the spinel lithium-rich lithium manganate cathode material of tin of double sintering legal system
CN117276515A (en) High-nickel ternary positive electrode material and preparation method and application thereof
CN110518210A (en) A kind of method and its material promoting rich lithium ternary material cyclical stability and capacity
CN1234180C (en) Modifying method for lithium ion cell positive pole material LiMn2O4
CN1461064A (en) Method for preparing lithium manganese oxide by using low-heat solid phase reaction
CN1674178A (en) Composite oxide electrode material and producing method thereof, and mixed super capacitor

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080402

Termination date: 20141111

EXPY Termination of patent right or utility model