CN103500831B - Anion doped manganese based solid solution positive electrode and preparation method - Google Patents

Anion doped manganese based solid solution positive electrode and preparation method Download PDF

Info

Publication number
CN103500831B
CN103500831B CN201310498055.5A CN201310498055A CN103500831B CN 103500831 B CN103500831 B CN 103500831B CN 201310498055 A CN201310498055 A CN 201310498055A CN 103500831 B CN103500831 B CN 103500831B
Authority
CN
China
Prior art keywords
based solid
solid solution
manganese based
doped
preparation
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.)
Active
Application number
CN201310498055.5A
Other languages
Chinese (zh)
Other versions
CN103500831A (en
Inventor
曹余良
何巍
杨汉西
艾新平
苑丁丁
尚珂会
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.)
Wuhan University WHU
Original Assignee
Wuhan University WHU
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 Wuhan University WHU filed Critical Wuhan University WHU
Priority to CN201310498055.5A priority Critical patent/CN103500831B/en
Publication of CN103500831A publication Critical patent/CN103500831A/en
Application granted granted Critical
Publication of CN103500831B publication Critical patent/CN103500831B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to a kind of anion doped manganese based solid solution positive electrode, its general structure is Li [Li ( ( x+1 ) / ( 2+x ) )mn (x/ ( 2+x ) )m ( ( 1-x ) / ( x+2 ) )] O 2-my 2m/z, in formula, Y is Doped anions, and M is transition metal layer doped chemical, 0 & lt; X & lt; 1,0 & lt; M & lt; 0.2, z is the chemical valence of Doped anions Y.The preferred S of Y 2-, PO 4 3-, SiO 4 4-, BO 3 3-, SO 4 2-in one or more, transition metal layer doped chemical M is generally selected from Co, one or more anion in Ni, Fe, Cr.Doped chemical joins in manganese based solid solution material structure, forms more stable chemical bond with the position of stable O in crystal structure, considerably improve crystal structural stability, thus obtain better electrochemical stability with O.

Description

Anion doped manganese based solid solution positive electrode and preparation method
Technical field
The invention belongs to anode material for lithium-ion batteries and preparation method field, be specifically related to anion doped manganese based solid solution positive electrode and preparation method thereof.
Background technology
Chemical power source is the key link of current great new energy technology development, and lithium ion battery, as the highest chemical energy storage system of energy density in current chemical power source, at mobile phone, achieves great success in the portable electronics market such as notebook.But commercial lithium ion battery is due to its positive electrode LiCoO instantly 2lower (the about 140mAhg of actual specific capacity -1), expensive, the factor such as poisonous, constrains it further at following electric automobile, the application of the great new forms of energy application such as energy-accumulating power station.Therefore, the study hotspot that anode material for lithium-ion batteries of future generation becomes new energy field is developed.Wherein, manganese based solid solution material due to specific capacity high (more than 250mAhg -1), with low cost, environmental friendliness receives the extensive concern of researchers.
Although manganese based solid solution material is the higher specific capacity of widespread reports in the literature, but because its electronic conductance is on the low side, result in its high rate performance poor, and capacity attenuation in cyclic process is very fast, these factors prevent the further large-scale application of manganese based solid solution material.A kind of mode improving this manganese based solid solution material property is under study for action ion doping.In manganese based solid solution material, O ion forms the framework of crystal by hexagonal closs packing, cation (Co, Ni, Mn etc.) be filled into cation formed framework space among, form hexagonal layered structure, the stability of O ion in lattice has very important impact to the stable of crystal framework.Laboratory, U.S. Argonne reports mixes F manganese based solid solution material Li (Li 0.2ni 0.15+0.5zco 0.10mn 0.55 0.5z) O 2 zf zchemical property, F doping is the alternative position of O ion in lattice, because transition-metal cation M and F has stronger bonding action, so can stable crystal structure, improve cycle performance, although the electrode material capacity after F process decreases, electrochemical stability and the thermal stability of this material are improved, and show the good application prospect of material.On the other hand, the doping principle of F ion is F doping is the alternative position of O ion in lattice, and F-O is without chemical bonding effect, and the raising of this doping way to structural stability is limited.
Summary of the invention
Technical problem to be solved by this invention provides a kind of anion doped manganese based solid solution positive electrode and preparation method thereof for above-mentioned prior art, by the position (O in non-proxy lattice) of O in the firm lattice of anion doped element to build more firm crystal framework, realize the object improving material electrochemical stability.
The present invention's adopted technical scheme that solves the problem is: a kind of anion doped manganese based solid solution positive electrode, its general structure is Li [Li ((x+1)/(2+x))mn (x/(2+x))m ((1-x)/(x+2))] O 2-my 2m/z, in formula, Y is Doped anions, and M is transition metal layer doped chemical, and 0<x<1,0<m<0.2, z are the chemical valence of Doped anions Y.
Particularly, described Doped anions Y is S 2-, PO 4 3-, SiO 4 4-, BO 3 3-, SO 4 2-in one or more, transition metal layer doped chemical M is one or more in Co, Ni, Fe, Cr.
Further with improvement, described doped chemical Y comprises F to such scheme -and S 2-, PO 4 3-, SiO 4 4-, BO 3 3-, SO 4 2-in one or more.
With S 2-, PO 4 3-, SiO 4 4-, BO 3 3-, SO 4 2-join in manganese based solid solution material structure Deng as doped chemical, formed and have the P-O more stablizing bond energy, S-O, Si-O, B-O key, P, S, Si, B element is the stable position of O ion in lattice in lattice, builds more stable crystal framework with this.
In order to enable doped chemical be incorporated into equably in material, the present invention adopts heat of polymerization solution to prepare anion doped manganese based solid solution positive electrode, and concrete steps are:
1) to LiOHH 2acrylic acid or acrylic acid derivative is dropwise added in the O aqueous solution, the mixed solution of the slaine of metallic element Mn, M contained by transition metal layer is added after mixing, the lithium salts of Y, ammonium salt or respective acids is added again after stirring, the i.e. obtained polymer monomer solution containing Y, the structure of polymer monomer is CH 2=C (R 1) COOM 1, R in formula 1for H or CH 3, M 1for Li, Mn, M;
2) add initator to step 1 containing in the polymer monomer solution of Y, in 60 ~ 100 DEG C of temperature ranges, carry out polymerization reaction, polymer is dried i.e. obtained polymer precursor;
3) carry out pyrolytic reaction to the polymer precursor of step 2, after compressing tablet, namely high-temperature calcination obtains target product Li [Li again ((x+1)/(2+x))mn (x/(2+x))m ((1-x)/(x+2))] O 2-my 2m/z, in formula, Y is Doped anions, and M is transition metal layer doped chemical, and 0<x<1,0<m<0.2, z are the chemical valence of Doped anions Y.
Preferably, the slaine of metallic element Mn, M contained by the transition metal layer of described step 1 is the nitrate of each metallic element, acetate or oxalates.
Preferably, the initator of described step 2 is the one in hydrogen peroxide, persulfate and sulphite.
Particularly, the temperature of described step 3 pyrolytic reaction is 300 ~ 500 DEG C, and the temperature of calcination reaction is 600 ~ 1000 DEG C, and calcination time is 6 ~ 15 hours.
Compared with prior art, the invention has the advantages that: adopt anion as S 2-, PO 4 3-, SiO 4 4-, BO 3 3-, SO 4 2-join in manganese based solid solution material structure Deng as doped chemical, form more stable chemical bond with the position of stable O in crystal structure with O, considerably improve crystal structural stability, thus obtain better electrochemical stability.The method of polymerization pyrolysis is adopted to prepare doped with manganese based solid solution positive electrode, doped chemical is occur in the mode of atom mixing at blend step, thus mixed fully between doped chemical with material body element, improve doping effect, and preparation method is simple and easy to control, be convenient to promote.
Accompanying drawing explanation
Fig. 1 is LMO material and different proportion PO thereof in the embodiment of the present invention 1 4 3-dopant material, first all charging and discharging curve figure under 30mA/g current density.
Fig. 2 is LMO material and different proportion PO thereof in the embodiment of the present invention 1 4 3-dopant material is 50 weeks cyclic curve figure under 30mA/g current density.
Fig. 3 is LMO material and PFLMO material 30 weeks cyclic curve figure under 100mA/g current density in the embodiment of the present invention 2.
Fig. 4 is LMO material and P-B-LMO material 50 weeks cyclic curve figure under 100mA/g current density in the embodiment of the present invention 3.
LMO material and Si-F-LMO material 50 weeks cyclic curve figure under 100mA/g current density in Fig. 5 embodiment of the present invention 4.
Embodiment
Below in conjunction with accompanying drawing embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1
PO 4 3-doped with manganese based solid solution material Li [Li 0.2co 0.13ni 0.13mn 0.54] O 2-3x/2(PO 4) xthe preparation of (x=1%, 3%, 5%, 10%)
By 18.047gLiOHH 2o is water-soluble, more dropwise adds 50ml acrylic acid solution, the 13.235gCo (NO then will mixed 3) 2﹒ 6H 2o, 13.212gNi (NO 3) 2﹒ 6H 2o and 67.618gMn (NO 3) 2mixed solution adds wherein, after stirring, adds (the NH of corresponding proportion 4) H 2pO 4, finally add the 1ml5% ammonium persulfate initiator aqueous solution, initiated polymerization 2h at 80 DEG C, then polymer dried at 120 DEG C, namely obtain polymer precursor.Polymer precursor is pyrolysis 5h at 450 DEG C, after 10MPa pressure makes disk, calcines 12h and namely obtain target product Li [Li at 900 DEG C 0.2co 0.13ni 0.13mn 0.54] O 2-3x/2(PO 4) x(x=1%, 3%, 5%, 10%).
By prepared PO 4 3-doped with manganese based solid solution material Li [Li 0.2co 0.13ni 0.13mn 0.54] O 2-3x/2(PO 4) x(x=1%, 3%, 5%, 10%) with do not carry out anion doped naked material Li [Li 0.2co 0.13ni 0.13mn 0.54] O 2(after referred to as LMO) is assembled into 2016 type button cells and carries out electro-chemical test, and Fig. 1 is LMO material and different proportion PO thereof 4 3-dopant material, first all charging and discharging curve figure under 30mA/g current density, showing the first all charge/discharge specific capacities of LMO material in figure is 365/293, it is 346/297 that the first all charge/discharge specific capacities of different proportion dopant material are followed successively by, 335/286,330/256,272/222.Fig. 2 is LMO material and different proportion PO thereof 4 3-dopant material, 50 weeks cyclic curve figure under 30mA/g current density, in figure, result display LMO material 50 weeks capability retentions are 80%, and different proportion dopant material 50 weeks capability retentions are followed successively by 85.5%, 91.5%, 92%, 96.8%, PO 4 3-after doping, the electrochemical stability of material is significantly improved.
Embodiment 2
F -and PO 4 3-doped with manganese based solid solution material Li [Li 0.2co 0.13ni 0.13mn 0.54] O 1.98(PO 4) 0.01f 0.01preparation
By 18.547gLiOHH 2o, LiF are water-soluble, more dropwise add 50ml acrylic acid solution, then will close uniform 13.235gCo (NO 3) 2﹒ 6H 2o, 13.212gNi (NO 3) 2﹒ 6H 2o and 67.618gMn (NO 3) 2mixed solution adds wherein, after stirring, adds (the NH of corresponding proportion 4) H 2pO 4, finally add the 1ml5% ammonium persulfate initiator aqueous solution, initiated polymerization 2h at 100 DEG C, then polymer dried at 120 DEG C, namely obtain polymer precursor.Polymer precursor is pyrolysis 5h at 500 DEG C, after 10MPa pressure makes disk, calcines 6h and namely obtain target product Li [Li at 1000 DEG C 0.2co 0.13ni 0.13mn 0.54] O 1.98(PO 4) 0.01f 0.01
By prepared PO 4 3-doped with manganese based solid solution material Li [Li 0.2co 0.13ni 0.13mn 0.54] O 1.98(PO 4) 0.01f 0.01(being called for short P-F-LMO afterwards) with do not carry out anion doped naked material Li [Li 0.2co 0.13ni 0.13mn 0.54] O 2(after referred to as LMO) is assembled into 2016 type button cells and carries out electro-chemical test, Fig. 3 is the capacity circulating curve of LMOPF material and LMO material, under 100mA current density, P-F-LMO and LMO electrode can realize 242 respectively, 244mAh/g, after circulation in 30 weeks, the capability retention of P-F-LMO is up to being 93%, and the capability retention of LMO is 84%.
Embodiment 3
PO 4 3-, BO 3 3-codope manganese based solid solution material Li [Li 0.2co 0.13ni 0.13mn 0.54] O 1.97(BO 3) 0.01(PO 4) 0.01preparation
By 18.547gLiOHH 2o is water-soluble, more dropwise adds 50ml acrylic acid solution, then will close uniform 13.235gCo (NO 3) 2﹒ 6H 2o, 13.212gNi (NO 3) 2﹒ 6H 2o and 67.618gMn (NO 3) 2mixed solution adds wherein, after stirring, adds (the NH of corresponding proportion 4) H 2pO 4, NH 4b 5o 84H 2o, finally adds 1ml5% ammonium sulfite initiator solution, and then polymer is dried, namely obtained polymer precursor by initiated polymerization 2h at 60 DEG C at 120 DEG C.Polymer precursor is pyrolysis 5h at 300 DEG C, after 10MPa pressure makes disk, calcines 15h and namely obtain mark product Li [Li at 600 DEG C 0.2co 0.13ni 0.13mn 0.54] O 1.97(BO 3) 0.01(PO 4) 0.01.
By prepared PO 4 3-, BO 3 3-codope manganese based solid solution material Li [Li 0.2co 0.13ni 0.13mn 0.54] O 1.97(BO 3) 0.01(PO 4) 0.01(being called for short P-B-LMO afterwards) material Li naked with it [Li 0.2co 0.13ni 0.13mn 0.54] O 2(after referred to as LMO) is assembled into 2016 type button cells and carries out electro-chemical test, Fig. 4 is the capacity circulating curve of P-B-LMO and LMO material, under 100mA current density, P-B-LMO and LMO electrode can realize 218 respectively, 244mAh/g, after circulation in 50 weeks, the capability retention of P-B-LMO is up to being 97.9%, and the capability retention of LMO is 82%.
Embodiment 4
SiO 4 4-, F -codope manganese based solid solution Li [Li 0.2co 0.13ni 0.13mn 0.54] O 1.975(SiO 4) 0.01f 0.01preparation
By 18.547gLiOHH 2o, LiF are water-soluble, more dropwise add 50ml acrylic acid solution, the 13.235gCo (NO then will mixed 3) 2﹒ 6H 2o, 13.212gNi (NO 3) 2﹒ 6H 2o and 67.618gMn (NO 3) 2mixed solution adds wherein, after stirring, adds (the NH of corresponding proportion 4) 4siO 4, finally add 1ml hydrogen peroxide initator, initiated polymerization 2h at 80 DEG C, then polymer dried at 120 DEG C, namely obtain polymer precursor.Polymer precursor is pyrolysis 5h at 450 DEG C, after 10MPa pressure makes disk, calcines 12h and namely obtain mark product Li [Li at 900 DEG C 0.2co 0.13ni 0.13mn 0.54] O 1.975(SiO 4) 0.01f 0.01.
By prepared PO 4 3-doped with manganese based solid solution material Li [Li 0.2co 0.13ni 0.13mn 0.54] O 1.975(SiO 4) 0.01f 0.01(being called for short Si-F-LMO afterwards) material Li naked with it [Li 0.2co 0.13ni 0.13mn 0.54] O 2(after referred to as LMO) is assembled into 2016 type button cells and carries out electro-chemical test, and Fig. 5 is the capacity circulating curve of Si-F-LMO material and LMO material.Under 100mA current density, Si-F-LMO and LMO can realize 220,244mAh/g respectively, and through the circulation of 50 weeks, the capability retention of Si-F-LMO was up to being 94%, and the capability retention of LMO is 82%.

Claims (5)

1. an anion doped manganese based solid solution positive electrode, is characterized in that: structural formula is Li [Li 0.2co 0.13ni 0.13mn 0.54] O 2-3x/2(PO 4) x(x=1%, 3%, 5%, 10%),
Or Li [Li 0.2co 0.13ni 0.13mn 0.54] O 1.98(PO 4) 0.01f 0.01,
Or Li [Li 0.2co 0.13ni 0.13mn 0.54] O 1.97(BO 3) 0.01(PO 4) 0.01,
Or Li [Li 0.2co 0.13ni 0.13mn 0.54] O 1.975(SiO 4) 0.01f 0.01.
2. prepare a method for anion doped manganese based solid solution positive electrode according to claim 1, it is characterized in that: comprise the steps:
1) to LiOHH 2acrylic acid or acrylic acid derivative is dropwise added in the O aqueous solution, the mixed solution of the slaine of metallic element Mn and M contained by transition metal layer is added after mixing, M is Co and Ni, and add the lithium salts of Doped anions Y, ammonium salt or respective acids after stirring again, Y corresponds to PO respectively 4 3-, F -and PO 4 3-, PO 4 3-and BO 3 3-, SiO 4 4-and F -, i.e. the obtained polymer monomer solution containing Y, the structure of polymer monomer is CH 2=C (R 1) COOM 1, R in formula 1for H or CH 3, M 1for Li, Mn and M;
2) add initator to step 1 containing in the polymer monomer solution of Y, in 60 ~ 100 DEG C of temperature ranges, carry out polymerization reaction, polymer is dried i.e. obtained polymer precursor;
3) carry out pyrolytic reaction to the polymer precursor of step 2, after compressing tablet, namely high-temperature calcination obtains the anion doped manganese based solid solution product of object construction formula again.
3. preparation method according to claim 2, is characterized in that: the slaine of metallic element Mn, M contained by the transition metal layer of described step 1 is the nitrate of each metallic element, acetate or oxalates.
4. preparation method according to claim 2, is characterized in that: the initator of described step 2 is the one in hydrogen peroxide, persulfate and sulphite.
5. preparation method according to claim 2, is characterized in that: the temperature of described step 3 pyrolytic reaction is 300 ~ 500 DEG C, and the temperature of calcination reaction is 600 ~ 1000 DEG C, and calcination time is 6 ~ 15 hours.
CN201310498055.5A 2013-10-22 2013-10-22 Anion doped manganese based solid solution positive electrode and preparation method Active CN103500831B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310498055.5A CN103500831B (en) 2013-10-22 2013-10-22 Anion doped manganese based solid solution positive electrode and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310498055.5A CN103500831B (en) 2013-10-22 2013-10-22 Anion doped manganese based solid solution positive electrode and preparation method

Publications (2)

Publication Number Publication Date
CN103500831A CN103500831A (en) 2014-01-08
CN103500831B true CN103500831B (en) 2016-03-30

Family

ID=49866017

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310498055.5A Active CN103500831B (en) 2013-10-22 2013-10-22 Anion doped manganese based solid solution positive electrode and preparation method

Country Status (1)

Country Link
CN (1) CN103500831B (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106229502B (en) * 2016-09-24 2019-06-25 上海大学 A kind of preparation method of the lithium-rich anode material of sulfide doping
CN107093713A (en) * 2017-04-07 2017-08-25 武汉大学 A kind of anion doped sodium-ion battery oxide anode material
CN108232186B (en) * 2017-12-25 2020-10-27 中国科学院化学研究所 Preparation method of single crystal particles and application of single crystal particles in secondary battery
CN108417791A (en) * 2018-01-31 2018-08-17 电子科技大学 Sulfate radical adulterates the preparation method of lithiumation molybdenum trioxide positive electrode
CN109638275B (en) * 2018-12-17 2021-10-15 中科廊坊过程工程研究院 Selenium and silicate co-doped high-nickel cathode material and preparation method and application thereof
CN109616658B (en) * 2018-12-17 2021-10-19 中科廊坊过程工程研究院 Selenium and sulfate radical co-doped high-nickel cathode material and preparation method and application thereof
CN111916725B (en) * 2019-05-08 2023-05-02 中国石油化工股份有限公司 Phosphorus-doped high-nickel cathode material for lithium battery and preparation process thereof
CN114068911B (en) * 2020-07-30 2023-06-20 巴斯夫杉杉电池材料有限公司 Modified high-nickel positive electrode material and preparation method thereof
CN112652771B (en) * 2020-12-22 2021-12-14 北京理工大学重庆创新中心 Polyanion-doped single-crystal high-nickel positive electrode material and preparation method thereof
CN113422041A (en) * 2021-07-05 2021-09-21 中国科学院过程工程研究所 Positive electrode material and preparation method and application thereof
CN114242969B (en) * 2021-11-18 2024-04-26 广州大学 Layered cobalt-free manganese-based lithium ion battery anode material and preparation method and application thereof
CN114122405B (en) * 2022-01-20 2022-05-13 武汉大学 High-performance lithium ion battery cathode material with stable structure and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102130325A (en) * 2011-01-26 2011-07-20 郭兆靖 Modified lithium manganate and synthesis method thereof
CN102244257A (en) * 2011-06-15 2011-11-16 清华大学深圳研究生院 High-temperature manganic acid lithium cathode material and preparation method thereof
CN103199229A (en) * 2013-03-19 2013-07-10 南开大学 Polyanion-doped lithium-enriched layered oxide anode material as well as preparation and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010029745A1 (en) * 2008-09-10 2010-03-18 戸田工業株式会社 Li-Ni COMPOSITE OXIDE PARTICLE POWDER FOR NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY AND METHOD FOR PRODUCTION THEREOF, AND NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY
WO2011025823A1 (en) * 2009-08-25 2011-03-03 A123 Systems, Inc. Mixed metal olivine electrode materials for lithium ion batteries having improved specific capacity and energy density

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102130325A (en) * 2011-01-26 2011-07-20 郭兆靖 Modified lithium manganate and synthesis method thereof
CN102244257A (en) * 2011-06-15 2011-11-16 清华大学深圳研究生院 High-temperature manganic acid lithium cathode material and preparation method thereof
CN103199229A (en) * 2013-03-19 2013-07-10 南开大学 Polyanion-doped lithium-enriched layered oxide anode material as well as preparation and application thereof

Also Published As

Publication number Publication date
CN103500831A (en) 2014-01-08

Similar Documents

Publication Publication Date Title
CN103500831B (en) Anion doped manganese based solid solution positive electrode and preparation method
CN103928672B (en) A kind of positive electrode active material for lithium ion battery and preparation method thereof
CN105958032B (en) A kind of method and application improving zinc ferrite chemical property by doping nickel element
CN109244443A (en) Lithium ion battery negative material and nonaqueous electrolyte battery
CN107437619A (en) A kind of anode for lithium battery material and preparation method thereof
CN104577088A (en) Lithium molybdate serving as secondary battery electrode material
CN106910888A (en) A kind of potassium/Prussian blue secondary cell
CN105720304A (en) Nonaqueous electrolyte and lithium-ion battery
CN102569773B (en) Anode material for lithium-ion secondary battery and preparation method thereof
CN104393234A (en) Modified lithium ion battery composite positive pole material and preparation method thereof
CN103915649A (en) High-energy-density lithium ion battery and preparation method thereof
CN104409685A (en) Lithium ion cell cathode material with core shell structure and preparation method thereof
CN104795555A (en) Aqueous-solution sodium-ion battery and cathode material, preparation method and application thereof
CN104157844A (en) High magnifying power lithium-rich manganese-based cathode material with nano/microstructure
CN103825014B (en) A kind of preparation method of high-voltage anode material of lithium ion batteries lithium nickel manganese composite oxide
CN103956491B (en) A kind of lithium ion battery positive pole material phosphoric acid ferrimanganic lithium and preparation method thereof
CN105470468A (en) Fluorine-doped lithium ferric manganese phosphate cathode material and preparation method thereof
CN104868110A (en) Graphene-oriented mesoporous Co2V2O7 nanosheet material and production method and application thereof
CN100537418C (en) Preparation method of transition element doped iron lithium phosphate powder
CN103022484B (en) Lithium iron conductive complex modified lithium iron phosphate anode material and preparation method thereof
CN105185978A (en) Manganese-containing oxygen compound used as negative active substance, and preparation method and use thereof
CN105161714A (en) Calcium-doped ternary positive electrode material of lithium ion battery and preparation method thereof
CN106328923A (en) Preparation method of positive electrode material of lithium battery
CN105406071A (en) High-rate lithium vanadium phosphate positive electrode material, and preparation method and application thereof
CN102683698B (en) Preparation method of conductive modified lithium iron phosphate

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