CN105322148A - Ion group induced composite phase modified lithium-rich laminated positive electrode material - Google Patents

Ion group induced composite phase modified lithium-rich laminated positive electrode material Download PDF

Info

Publication number
CN105322148A
CN105322148A CN201510661762.0A CN201510661762A CN105322148A CN 105322148 A CN105322148 A CN 105322148A CN 201510661762 A CN201510661762 A CN 201510661762A CN 105322148 A CN105322148 A CN 105322148A
Authority
CN
China
Prior art keywords
solution
rich lithium
cathode material
positive electrode
layered cathode
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
CN201510661762.0A
Other languages
Chinese (zh)
Other versions
CN105322148B (en
Inventor
赵乃勤
郭立超
师春生
刘恩佐
何春年
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.)
Tianjin University
Original Assignee
Tianjin University
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 Tianjin University filed Critical Tianjin University
Priority to CN201510661762.0A priority Critical patent/CN105322148B/en
Priority to PCT/CN2015/093105 priority patent/WO2017063233A1/en
Publication of CN105322148A publication Critical patent/CN105322148A/en
Application granted granted Critical
Publication of CN105322148B publication Critical patent/CN105322148B/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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • 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

Abstract

The invention relates to an ion group induced composite phase modified lithium-rich laminated positive electrode material. The lithium-rich laminated positive electrode material comprises an inner layer, an outer thin layer, and a middle layer, wherein the inner layer is the lithium-rich laminated positive electrode material with the grain diameter of 50-200 nm; the outer thin layer is molybdenum oxide partially substituted by sulfate radical; the middle layer formed by a spinel phase region and a composite phase region that are generated in an in-situ reaction between thiomolybdate and the lithium-rich phase Li2MnO3 on the surface of the lithium-rich laminated positive electrode material, and the middle layer is between the inner layer and the outer thin layer; the thickness of the outer thin layer is less than 5 nm; and the thickness of the middle layer is 10-30 nm. The invention also provides the preparation method for the positive electrode material. The modifying material is less in dosage, the technological operation is simple, and the structural controllability is high; and in addition, the prepared composite phase modified lithium-rich laminated positive electrode material has better electrochemical performance.

Description

The rich lithium layered cathode material that ionic group induction compound phase is modified
Technical field
The present invention relates to the rich lithium layered cathode material Li that a kind of reproducibility ionic group induced surface spinelle changes 1.2mn 0.54ni 0.13co 0.13o 2and preparation method, belong to the technology of preparing of nano composite material.
Background technology
Green clean energy resource and energy conversion device thereof progressively replace non-renewable energy resources and dynamical system, in this energy revolution, lithium ion battery, with its higher energy density and technological design flexibly, is applied in large-scale power grid energy storage device, power vehicle energy supplying system.But the flying power of lithium-ion electric electrical automobile, can not meet actual needs far away, one of main restricting factor is that the specific capacity of anode material for lithium-ion batteries itself is lower.Therefore, the positive electrode that a kind of theoretical specific capacity is higher---rich lithium layered cathode material Li 2mnO 3liMO 2(M=Co, Ni, Mn, Fe, Ru ...)---be subject to the great attention of researcher.Relative to traditional LiCoO 2and LiFePO 4although rich lithium material specific capacity is higher, but its high rate performance is poor, cannot meet the requirement of high power density.In order to address this problem, people attempt the conductivity being improved rich lithium material by finishing, and wherein, Surface coating is the Main Means of finishing.At present, there is the phosphate (FePO of electro-chemical activity 4, AlPO 4deng), lithium manganate having spinel structure, carbon (Graphene, carbon pipe, acetylene black etc.) becomes and improves the main clad material of high rate performance; If above-mentioned material forms even clad structure, often need accurately to control reaction rate, the controllability of operation is more weak.So, be necessary to find a kind of controllability strong, operate the process for modifying surface that simple and easy and finishing comes from original position phase in version mutually.
Summary of the invention
The object of the invention is rich lithium layered cathode material and the preparation method of the compound phase finishing providing a kind of reproducibility ionic group induced surface spinelle to change, the method advantage is that decorative material use amount is few, technological operation is simple, structural controllability is strong, and obtained composite modified rich lithium layered cathode material has better chemical property.
The present invention is achieved by the following technical solutions.
The rich lithium layered cathode material that a kind of ionic group induction compound phase is modified, it is characterized in that, the composition of this rich lithium layered cathode material is, internal layer is the rich lithium layered cathode material of particle diameter 50 ~ 200nm, outer thin layer is the molybdenum oxide that sulphate moiety replaces, and is the rich lithium phase Li on thiomolybdate and rich lithium layered cathode material surface between internal layer with outer thin layer 2mnO 3the intermediate layer of the spinelle phase region that reaction in-situ generates and compound phase region composition; Outer thickness of thin layer is less than 5nm, and intermediate layer thickness is 10 ~ 30nm.
The preparation method of the rich lithium layered cathode material that above-mentioned compound phase is modified, comprises the following steps:
1) sol-gal process prepares rich lithium layered cathode material Li 1.2mn 0.54ni 0.13co 0.13o 2
Under mechanical stirring, first by Ni (CH 3cOO) 24H 2o, Co (CH 3cOO) 24H 2o, Mn (CH 3cOO) 24H 2o and LiCH 3cOO is followed successively by 0.13:0.13:0.54:(1.21 ~ 1.25 by the mol ratio of metal ion) be dissolved in deionized water, being made into metal total ion concentration is that the solution of 0.5 ~ 2.5mol/L is denoted as solution A, be dissolved in by citric acid in deionized water, being mixed with concentration is that the solution of 0.5 ~ 2.0mol/L is denoted as solution B, and citric acid is (0.8 ~ 1.2) with the ratio of the amount of substance of nickel ion in solution A: 0.13, solution B is dropwise joined in solution A, and drip ammoniacal liquor and regulate mixed solution pH value to be 7.1 ~ 7.8, afterwards mixed solution is placed in 80 DEG C of water bath with thermostatic control reaction 4 ~ 7h, obtain semigel, by semigel at 100 ~ 120 DEG C of drying 12 ~ 24h, obtain xerogel, be placed in box type furnace, with ramp to 450 ~ 500 DEG C of 5 ~ 10 DEG C/min, insulation 3 ~ 5h, the powder obtained after being cooled to room temperature is placed in tube furnace again, in air atmosphere, with the ramp to 800 DEG C of 5 ~ 10 DEG C/min, insulation 16 ~ 20h, be cooled to room temperature and obtain rich lithium layered cathode material Li 1.2mn 0.54ni 0.13co 0.13o 2,
2) Ammonium Molybdate Tetrahydrate is dissolved in deionized water, be mixed with 2 ~ 2.5gL -1ammonium molybdate aqueous solution, according to Li 1.2co 0.13ni 0.13mn 0.54o 2be (4 ~ 6) with the mass ratio of Ammonium Molybdate Tetrahydrate: 1, by step 1) gained Li 1.2co 0.13ni 0.13mn 0.54o 2join in this ammonium molybdate aqueous solution, fully ultrasonic 5 ~ 10min, ammonium molybdate and Li 1.2co 0.13ni 0.13mn 0.54o 2the fully contact of primary particle surface;
3) being that 40 ~ 48% ammonium sulfide solutions are added drop-wise to step 2 by mass fraction) in the suspension-turbid liquid of gained, wherein ammonium sulfide solution and suspension-turbid liquid volume ratio are (0.8 ~ 1.2): 100, stir 12 ~ 24h; Suction filtration, dry, gained powder is placed in tube furnace, at 300 ~ 400 DEG C of insulation 1h, is cooled to the Li that room temperature obtains compound phase modification 1.2co 0.13ni 0.13mn 0.54o 2.
The present invention has the following advantages and effect: step of preparation process is simple, the thiomolybdate that induced surface Spinel changes is ionic group, fully contact with rich lithium material primary particle surface in aqueous, avoid the problem that heterogeneous reducing agent spontaneously cannot be dispersed in rich lithium material particle surface.The rich lithium layered cathode material that prepared compound phase is modified, the molybdenum oxide layer of sulfate radical doping is evenly coated on the primary particle surface of rich lithium layered cathode material, as physical protection layer; Spinelle phase region is generated and transition phase region forms good ion transport layers by thiomolybdate and primary particle surface reaction.Double-deck (physical protection layer and In-suit spinel phase in version layer) composite phase-structured, make material while high rate performance promotes, larger current density charge and discharge cycles test chart reveals excellent capability retention.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph that the embodiment of the present invention 1 obtains the rich lithium layered cathode material that compound phase is modified.
Fig. 2 is the high-resolution-ration transmission electric-lens photo that the embodiment of the present invention 1 obtains the surface and interface of the rich lithium layered cathode material that compound phase is modified.
Fig. 3 is the distribution diagram of element that the embodiment of the present invention 1 obtains the surface and interface of the rich lithium layered cathode material that compound phase is modified.
Fig. 4 is the X-ray diffraction contrast collection of illustrative plates of the embodiment of the present invention 1 and blank sample.
Fig. 5 is the high rate performance curve that the embodiment of the present invention 1 obtains the rich lithium layered cathode material that compound phase is modified.
Fig. 6 is rich lithium layered cathode material and the cycle performance comparison diagram of blank sample under different current density that the embodiment of the present invention 1 obtains compound phase modification.
Embodiment
Below in conjunction with embodiment, the invention will be further described, and these embodiments, just for illustration of the present invention, do not limit the present invention.
Embodiment 1:
1) 1.6887gNi (CH is taken 3cOO) 24H 2o, 1.6647gCo (CH 3cOO) 24H 2o, 6.6100gMn (CH 3cOO) 24H 2o and 6.3067gLiCH 3cOO is dissolved in 100mL deionized water, is denoted as solution A; 10.5598g citric acid is dissolved in 60mL deionized water, is denoted as solution B.Solution B dropwise joins in solution A, Keep agitation 15min, dripping ammoniacal liquor regulation system pH value is 7.5, after continuing to stir 15min, 80 DEG C of water bath with thermostatic control 4 ~ 5h, obtain darkviolet viscous fluid, and this liquid rotating moves in crucible, at 120 DEG C of dry 24h, be placed in box type furnace, with the ramp to 480 DEG C of 10 DEG C/min, insulation 2h, presintering gained powder is placed at tube furnace, air atmosphere, with the ramp to 800 DEG C of 10 DEG C/min, insulation 20h, take out immediately after holding stage terminates and cool fast in air at room temperature, obtain rich lithium layered cathode material Li 1.2mn 0.54ni 0.13co 0.13o 2.
2) 0.11g Ammonium Molybdate Tetrahydrate is dissolved in 60mL deionized water, step 1) gained Li 1.2co 0.13ni 0.13mn 0.54o 2taking 0.5g joins in this ammonium molybdate aqueous solution, ultrasonic 10min, stirs;
3) 0.05mL ammonium sulfide solution is added drop-wise to step 2) in the suspension-turbid liquid of gained, stir 12h; Suction filtration, dry, gained powder is placed in tube furnace, under air atmosphere, with the ramp to 400 DEG C of 10 DEG C/min, at 400 DEG C of insulation 1h, is cooled to the Li that room temperature obtains compound phase modification 1.2co 0.13ni 0.13mn 0.54o 2.
The rich lithium layered cathode material of the compound phase finishing that said process is obtained, acetylene black, poly-inclined tetrafluoroethene, the mass ratio being 8:1:1 according to mass ratio is dissolved in 1-METHYLPYRROLIDONE, mechanical agitation 3 ~ 5h makes slurry, be coated on aluminium foil with I-shaped scraper, 80 DEG C of vacuumize 24h.Pole piece is die-cut into the disk that diameter is 12mm, with it for work electrode, burying paper tinsel with metal is to electrode, and barrier film adopts Celgard2325 diaphragm paper, and electrolyte adopts the LiPF of 1mol/L 6eC:EMC:DEC=1:1:1 (volume ratio) solution, in glove box assembled battery.Carry out circulation and high rate performance test at LANDt battery test system, performance curve is shown in Fig. 5 and Fig. 6.
Embodiment 2:
1) to 2) step is identical with embodiment 1.
3) 0.04mL ammonium sulfide solution is added drop-wise to step 2) in the suspension-turbid liquid of gained, stir 12h; Suction filtration, dry, gained powder is placed in tube furnace, under air atmosphere, with the ramp to 350 DEG C of 10 DEG C/min, at 350 DEG C of insulation 1h, is cooled to the Li that room temperature obtains compound phase modification 1.2co 0.13ni 0.13mn 0.54o 2.
Embodiment 3:
1) to 2) step is identical with embodiment 1.
3) 0.05mL ammonium sulfide solution is added drop-wise to step 2) in the suspension-turbid liquid of gained, stir 12h; Suction filtration, dry, gained powder is placed in tube furnace, under air atmosphere, with the ramp to 350 DEG C of 10 DEG C/min, at 350 DEG C of insulation 1h, is cooled to the Li that room temperature obtains compound phase modification 1.2co 0.13ni 0.13mn 0.54o 2.
Blank sample:
Take 1.6887gNi (CH 3cOO) 24H 2o, 1.6647gCo (CH 3cOO) 24H 2o, 6.6100gMn (CH 3cOO) 24H 2o and 6.3067gLiCH 3cOO is dissolved in 100mL deionized water, is denoted as solution A; 10.5598g citric acid is dissolved in 60mL deionized water, is denoted as solution B.Solution B dropwise joins in solution A, Keep agitation 15min, dripping ammoniacal liquor regulation system pH value is 7.5, after continuing to stir 15min, 80 DEG C of water bath with thermostatic control 4 ~ 5h, obtain darkviolet viscous fluid, and this liquid rotating moves in crucible, at 120 DEG C of dry 24h, be placed in box type furnace, with the ramp to 480 DEG C of 10 DEG C/min, insulation 2h, presintering gained powder is placed at tube furnace, air atmosphere, with the ramp to 800 DEG C of 10 DEG C/min, insulation 20h, take out immediately after holding stage terminates and cool fast in air at room temperature, obtain rich lithium layered cathode material Li 1.2mn 0.54ni 0.13co 0.13o 2, be blank sample.

Claims (2)

1. the rich lithium layered cathode material of ionic group induction compound phase modification, it is characterized in that, the composition of this rich lithium layered cathode material is, internal layer is the rich lithium layered cathode material of particle diameter 50 ~ 200nm, outer thin layer is the molybdenum oxide that sulphate moiety replaces, and is the rich lithium phase Li on thiomolybdate and rich lithium layered cathode material surface between internal layer with outer thin layer 2mnO 3the intermediate layer of the spinelle phase region that reaction in-situ generates and compound phase region composition; Outer thickness of thin layer is less than 5nm, and intermediate layer thickness is 10 ~ 30nm.
2. a preparation method for the rich lithium layered cathode material of ionic group induction compound phase modification, comprises the following steps:
1) sol-gal process prepares rich lithium layered cathode material Li 1.2mn 0.54ni 0.13co 0.13o 2
Under mechanical stirring, first by Ni (CH 3cOO) 24H 2o, Co (CH 3cOO) 24H 2o, Mn (CH 3cOO) 24H 2o and LiCH 3cOO is followed successively by 0.13:0.13:0.54:(1.21 ~ 1.25 by the mol ratio of metal ion) be dissolved in deionized water, being made into metal total ion concentration is that the solution of 0.5 ~ 2.5mol/L is denoted as solution A, be dissolved in by citric acid in deionized water, being mixed with concentration is that the solution of 0.5 ~ 2.0mol/L is denoted as solution B, and citric acid is (0.8 ~ 1.2) with the ratio of the amount of substance of nickel ion in solution A: 0.13, solution B is dropwise joined in solution A, and drip ammoniacal liquor and regulate mixed solution pH value to be 7.1 ~ 7.8, afterwards mixed solution is placed in 80 DEG C of water bath with thermostatic control reaction 4 ~ 7h, obtain semigel, by semigel at 100 ~ 120 DEG C of drying 12 ~ 24h, obtain xerogel, be placed in box type furnace, with ramp to 450 ~ 500 DEG C of 5 ~ 10 DEG C/min, insulation 3 ~ 5h, the powder obtained after being cooled to room temperature is placed in tube furnace again, in air atmosphere, with the ramp to 800 DEG C of 5 ~ 10 DEG C/min, insulation 16 ~ 20h, be cooled to room temperature and obtain rich lithium layered cathode material Li 1.2mn 0.54ni 0.13co 0.13o 2,
2) Ammonium Molybdate Tetrahydrate is dissolved in deionized water, be mixed with 2 ~ 2.5gL -1ammonium molybdate aqueous solution, according to Li 1.2co 0.13ni 0.13mn 0.54o 2be (4 ~ 6) with the mass ratio of Ammonium Molybdate Tetrahydrate: 1, by step 1) gained Li 1.2co 0.13ni 0.13mn 0.54o 2join in this ammonium molybdate aqueous solution, fully ultrasonic 5 ~ 10min, ammonium molybdate and Li 1.2co 0.13ni 0.13mn 0.54o 2the fully contact of primary particle surface;
3) being that 40 ~ 48% ammonium sulfide solutions are added drop-wise to step 2 by mass fraction) in the suspension-turbid liquid of gained, wherein ammonium sulfide solution and suspension-turbid liquid volume ratio are (0.8 ~ 1.2): 100, stir 12 ~ 24h; Suction filtration, dry, gained powder is placed in tube furnace, at 300 ~ 400 DEG C of insulation 1h, is cooled to the Li that room temperature obtains compound phase modification 1.2co 0.13ni 0.13mn 0.54o 2.
CN201510661762.0A 2015-10-14 2015-10-14 The lithium-rich positive electrode of ionic group induction compound phase modification Active CN105322148B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201510661762.0A CN105322148B (en) 2015-10-14 2015-10-14 The lithium-rich positive electrode of ionic group induction compound phase modification
PCT/CN2015/093105 WO2017063233A1 (en) 2015-10-14 2015-10-28 Ionic group induced compound phase modified lithium-rich layered cathode material and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510661762.0A CN105322148B (en) 2015-10-14 2015-10-14 The lithium-rich positive electrode of ionic group induction compound phase modification

Publications (2)

Publication Number Publication Date
CN105322148A true CN105322148A (en) 2016-02-10
CN105322148B CN105322148B (en) 2017-12-01

Family

ID=55249111

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510661762.0A Active CN105322148B (en) 2015-10-14 2015-10-14 The lithium-rich positive electrode of ionic group induction compound phase modification

Country Status (2)

Country Link
CN (1) CN105322148B (en)
WO (1) WO2017063233A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106532037A (en) * 2017-01-13 2017-03-22 哈尔滨工业大学 Preparation method of vanadium-molybdenum-doped lithium ion battery cathode material
CN107834050A (en) * 2017-12-13 2018-03-23 江南大学 A kind of lithium-enriched cathodic material of lithium ion battery and its improved method
CN111816864A (en) * 2020-06-02 2020-10-23 广东工业大学 Lithium-rich layered oxide composite cathode material and preparation method and application thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN113353990B (en) * 2020-12-22 2023-07-25 厦门厦钨新能源材料股份有限公司 High-nickel positive electrode material, preparation method thereof and lithium ion battery
CN114335488B (en) * 2022-01-06 2023-03-10 中国科学技术大学 Coating modified lithium-rich manganese-based cathode material and preparation method thereof
CN117080535B (en) * 2023-10-19 2023-12-22 中创新航科技集团股份有限公司 Cylindrical battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070027985A (en) * 2005-08-30 2007-03-12 주식회사 엘지화학 Electrode active material having double layer structure and electrochemical device using the same
US20080299457A1 (en) * 2007-06-04 2008-12-04 Yoshiyuki Muraoka Nonaqueous electrolyte secondary battery and method for manufacturing positive electrode of nonaqueous electrolyte secondary battery
CN102306779A (en) * 2011-09-06 2012-01-04 上海交通大学 Lithium ion battery positive electrode material lithium-enriched doped lithium molybdate and preparation method thereof
CN103178261A (en) * 2013-04-12 2013-06-26 长沙理工大学 In-situ synthesis method of fast ion conductor inlaid lithium ion battery cathode material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5425505B2 (en) * 2009-03-27 2014-02-26 三洋電機株式会社 Lithium ion secondary battery
JP5791877B2 (en) * 2009-09-30 2015-10-07 三洋電機株式会社 Positive electrode active material, method for producing the positive electrode active material, and nonaqueous electrolyte secondary battery using the positive electrode active material
CN102244259A (en) * 2011-06-17 2011-11-16 中国科学院化学研究所 Composite lithium-rich anode material, its preparation method and its application
CN102916169B (en) * 2012-10-26 2015-05-13 中国科学院宁波材料技术与工程研究所 Lithium-rich manganese-based anode material and method for manufacturing same
CN103280574A (en) * 2013-05-29 2013-09-04 上海电力学院 Lithium-enriched ternary anode material of power lithium-ion battery and preparation method of lithium-enriched ternary anode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070027985A (en) * 2005-08-30 2007-03-12 주식회사 엘지화학 Electrode active material having double layer structure and electrochemical device using the same
US20080299457A1 (en) * 2007-06-04 2008-12-04 Yoshiyuki Muraoka Nonaqueous electrolyte secondary battery and method for manufacturing positive electrode of nonaqueous electrolyte secondary battery
CN102306779A (en) * 2011-09-06 2012-01-04 上海交通大学 Lithium ion battery positive electrode material lithium-enriched doped lithium molybdate and preparation method thereof
CN103178261A (en) * 2013-04-12 2013-06-26 长沙理工大学 In-situ synthesis method of fast ion conductor inlaid lithium ion battery cathode material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
吴承仁，等: "锂离子电池用富锂层状正极材料", 《化学进展》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106532037A (en) * 2017-01-13 2017-03-22 哈尔滨工业大学 Preparation method of vanadium-molybdenum-doped lithium ion battery cathode material
CN107834050A (en) * 2017-12-13 2018-03-23 江南大学 A kind of lithium-enriched cathodic material of lithium ion battery and its improved method
CN111816864A (en) * 2020-06-02 2020-10-23 广东工业大学 Lithium-rich layered oxide composite cathode material and preparation method and application thereof

Also Published As

Publication number Publication date
WO2017063233A1 (en) 2017-04-20
CN105322148B (en) 2017-12-01

Similar Documents

Publication Publication Date Title
CN105322148A (en) Ion group induced composite phase modified lithium-rich laminated positive electrode material
CN110474044A (en) A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof
CN102956895B (en) Positive electrode that surface recombination is coated and preparation method thereof and lithium ion battery
CN104681809B (en) The method of modifying of lithium-rich manganese-based anode material
CN102509786B (en) Porous metal oxide-carbon composite thin film electrode and preparation method thereof
CN104009252A (en) Sodium-ion battery and preparation method thereof
CN104538207A (en) Method for preparing titanium niobate and carbon nanotube composite material and lithium ion capacitor with material as negative electrode
CN102376927B (en) Lithium ion battery protecting film and lithium ion battery current collector applying same as well as lithium ion battery
CN110400929A (en) A kind of metal-doped ternary positive electrode active material of Phosphate coating and its preparation and application
Song et al. Enhanced electrochemical performance of Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 cathode material with bamboo essential oil
CN110078121A (en) A kind of preparation method and application of Magnesium ion battery vanadic anhydride positive electrode
JP7414702B2 (en) Cathode active material for lithium secondary batteries
CN107681147A (en) A kind of preparation method of solid electrolyte coating modification anode material for lithium-ion batteries and application
CN107069032A (en) A kind of preparation method of lithium ion battery hollow ball shape lithium-rich manganese-based anode material
Song et al. Effect of drying temperature on properties of lithium-rich manganese-based materials in sol-gel method
CN108598463B (en) Preparation method of nano flaky lithium-rich manganese-based positive electrode material
CN102332582B (en) Preparation method for novel lithium vanadium phosphate/bamboo charcoal composite cathode material
CN104201342A (en) Method for improving physical property of lithium and manganese enriched lithium ion battery pole pieces
CN105826568A (en) Lithium-rich positive electrode material with hypoxic metallic oxide coating layer structure, preparation method and application
CN102569765B (en) Composite anode material for lithium ion battery and preparation method thereof
CN102376958B (en) Modifier for lithium ion batteries, and preparation method and application thereof
CN108682847B (en) Multi-shell hollow microspherical alpha-Fe2O3Material, preparation method and application thereof
Cai et al. Synthesis and electrochemical performance of nanosheet lamellar ZnMn2O4 anodes for Li-ion batteries by microwave hydrothermal method
CN107834054B (en) Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery
CN113387385B (en) Preparation method and application of two-dimensional amorphous molybdenum-based oxide composite material with oxygen-rich vacancy defects

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP02 Change in the address of a patent holder
CP02 Change in the address of a patent holder

Address after: 300350 District, Jinnan District, Tianjin Haihe Education Park, 135 beautiful road, Beiyang campus of Tianjin University

Patentee after: Tianjin University

Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92

Patentee before: Tianjin University