CN101276913A - Method for preparing lithium cobaltate composite electrode material coated by iron phosphate - Google Patents

Method for preparing lithium cobaltate composite electrode material coated by iron phosphate Download PDF

Info

Publication number
CN101276913A
CN101276913A CNA2008101120999A CN200810112099A CN101276913A CN 101276913 A CN101276913 A CN 101276913A CN A2008101120999 A CNA2008101120999 A CN A2008101120999A CN 200810112099 A CN200810112099 A CN 200810112099A CN 101276913 A CN101276913 A CN 101276913A
Authority
CN
China
Prior art keywords
electrode material
licoo
composite electrode
iron phosphate
solution
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
CNA2008101120999A
Other languages
Chinese (zh)
Other versions
CN100565985C (en
Inventor
杨文胜
李刚
杨占旭
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.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
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 Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CNB2008101120999A priority Critical patent/CN100565985C/en
Publication of CN101276913A publication Critical patent/CN101276913A/en
Application granted granted Critical
Publication of CN100565985C publication Critical patent/CN100565985C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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

Abstract

The invention relates to the preparation method of an iron phosphate coating lithium cobalt oxide composite electrode material, which belongs to the lithium ion battery electrode material and the preparation technology field. The preparation technology of the invention is that: a LiCoO2 is added into a Fe(NO3)3 solution, then an ultrasound dispersive treatment is carried out for the solution, under a mechanical agitation, a (NH4)2HPO4 solution is slowly dropped into the solution, after filtration, wash and heat treatment, the iron phosphate coating lithium cobalt composite electrode material is obtained. The invention has the advantages of having simple preparation process, good coating effect, and having good electrochemistry circulation stability and charge-off-resistant properties under the condition that the composite electrode material obtained does not reduce the specific discharge capacity of the lithium cobalt oxide.

Description

A kind of preparation method of lithium cobaltate composite electrode material coated by iron phosphate
Technical field
The invention belongs to lithium ion battery electrode material and preparing technical field thereof, a kind of ferric phosphate FePO particularly is provided 4Coat cobalt acid lithium LiCoO 2The preparation method of combination electrode material.
Background technology
Has α-NaFeO 2The LiCoO of type layer structure 2Be at present unique industrialization and be widely used in the positive electrode of commercialization lithium ion battery on a large scale, and also will occupy dominant position for a comparatively long period of time.But LiCoO 2Cost an arm and a leg, actual specific capacity 120～140mAh/g only is about 50% of its theoretical specific capacity 274mAh/g.When the charging cut-ff voltage of lithium ion battery is higher than 4.2V, LiCoO 2A large amount of Co in the structure 3+Will become Co 4+, Co 4+Formation will cause the formation of oxygen defect, the binding force that this will weaken between transition metals cobalt and the oxygen makes Co 4+Be dissolved in the electrolyte, thereby destroy the positive electrode crystal structure, specific capacity is reduced rapidly.
In order to overcome the problems referred to above, the researcher mainly adopts two kinds of modified methods at present:
The first, adopt Ni, Al, Mg, Zr, Mn etc. carry out the part doped and substituted to Co, in the hope of reaching the purpose of stabilizing material structure.As at document (1) Journal of Power Sources, 2005, among the 148:90, human Zr-Mg such as H.Y.Xu partly replace Co and have synthesized LiCo 1-xZr X/2Mg X/2O 2Positive electrode, wherein LiCo 0.94Zr 0.03Mg 0.03O 2First discharge specific capacity be 144mAh/g, 20 times circulation back capability retention is 96%.Up to the present, many elements have been used to the doped and substituted of cobalt, and the structure of stabilizing material has been played certain positive role, but do not have obvious effect for the anti-over-charging electrical property that improves material.
The second, at LiCoO 2The surface coats Al 2O 3, MgO, ZnO, TiO 2, AlPO 4, LiMn 2O 4Deng material, directly contact between electrode material and the electrolyte preventing, slow down the dissolving of cobalt.As at document (2) Solid State Ionics, 2002, among the 152-153:341, human Al such as Xuejie Huang 2O 3To LiCoO 2Carry out surface coating modification, the material after the modification is 4.7V (vs.Li at the charging cut-ff voltage +/ first discharge specific capacity is 192mAh/g Li) time, and 20 times circulation back specific discharge capacity still remains on 187mAh/g, and capability retention is 97.6%, has electrochemistry cycle performance preferably.But, except LiMn 2O 4Beyond the clad material with electro-chemical activity, other is as Al 2O 3, MgO, metal oxides such as ZnO are the non-electrochemical active material, it adds the reduction that affiliation causes the electrode material reversible specific capacity.
At document (3) power technology, 2007,31 (5): in 372, people such as Wang Hong are with Fe (CH recently 3CO 2) 24H 2O and NH 4H 2PO 4Be raw material, at N 2Synthesized FePO under the atmosphere 4Coat LiCoO 2Composite material, the anti-over-charging electrical property of material has obtained certain raising.But, because at N 2Fe under the atmosphere 2+Can not be oxidized to Fe 3+So actual clad material should be mainly Fe 3(PO 4) 2LiCoO 2Under anoxia condition, carry out high-temperature roasting and handle, can make LiCoO 2Crystal structure suffer to a certain degree destruction, lost the specific discharge capacity of electrode material; In addition with expensive Fe (CH 3CO 2) 24H 2O is that raw material reaches at N 2Synthesize under the harsh conditions of protection, cost is higher.
Summary of the invention:
The purpose of this invention is to provide a kind of FePO 4Coat LiCoO 2Combination electrode material (FePO 4Mass fraction be the preparation method of 1wt.%～5wt.%), this method technology is simple, with low cost, and coating layer is even, controllable thickness, suitability for scale production.
The inventive method is with the cheaper Fe (NO of price 3) 39H 2O is a raw material, earlier with LiCoO 2Join Fe (NO 3) 3In the solution, after a period of time, under mechanical agitation, drip (NH through ultrasonic dispersion treatment 4) 2HPO 4Solution, after filtration, obtain FePO after the washing, heat treatment 4Coat LiCoO 2Combination electrode material.Concrete processing step is as follows:
A, with LiCoO 2And Fe (NO 3) 39H 2O joins in the deionized water in 7: 1～37: 1 ratio of mass ratio, is made into Fe 3+Concentration be the suspension-turbid liquid of 0.05～0.3mol/L, and be that to control its pH value be that 2.0～3.0 (acid solution is to LiCoO for the watery hydrochloric acid of 0.05～0.1mol/L by adding concentration 2Certain alligatoring effect is played on the surface, can increase LiCoO 2Specific area, help FePO 4The formation of coating layer.); In temperature is 20～40 ℃, and power is sonicated 15～60 minutes under the condition of 800～2000W/L; Then suspension-turbid liquid is transferred in the there-necked flask, mechanical agitation 30～90 minutes drips the (NH of 0.05～0.45mol/L again under mechanical agitation 4) 2HPO 4Solution continues to stir 30～90 minutes; The suspension-turbid liquid that obtains is filtered, and is 7～7.5 with the deionized water wash product to filtrate pH value, and filter cake is following dry 6～12 hours at 50～150 ℃.
B, steps A gained material is warming up to 350～550 ℃ with 2～10 ℃/min speed, and constant temperature 5～15 hours, naturally cool to room temperature then, obtain FePO 4Coat LiCoO 2Combination electrode material.
Using plasma atomic emission spectrum (ICP-AES) is to FePO 4Coat LiCoO 2Combination electrode material the analysis showed that, FePO 4Mass fraction in final products is between 1wt.%～5wt.%; X-ray diffraction (XRD) the analysis showed that final products have α-NaFeO 2The type layer structure does not have any impurity peaks, and FePO is described 4Coating is to LiCoO 2Body construction do not play any destruction; Field emission scanning electron microscope (FESEM) the analysis showed that LiCoO 2Particle surface has evenly coated one deck FePO 4, through the TEM (transmission electron microscope) analysis coating thickness between 50～250nm.
The synthetic FePO of the inventive method will be adopted 4Coat LiCoO 2Composite positive pole and commercially available acetylene black conductive agent and Kynoar (PVDF) binding agent mix by 90: 5: 5 mass ratio, and the thickness of compressing tablet to 30～70 μ m, in 120 ℃ of vacuum (＜10Pa) dry 24 hours.As negative pole, adopt Celgard 2400 barrier films, the LiPF of 1mol/L with metal lithium sheet 6+ EC+DMC (EC/DMC volume ratio 1: 1) is an electrolyte, at the German M. Braun Unlab of company type dry argon gas glove box (H 2O＜1ppm, O 2＜be assembled into Experimental cell in 1ppm), adopt the blue electric BTI1-10 type cell tester in Wuhan to carry out electrochemical property test.FePO by embodiment of the invention acquisition 4Coat LiCoO 2The chemical composition of sample, electro-chemical test condition, reversible specific discharge capacity, circulation first 10 times, 20 times, the reversible specific discharge capacity in the time of 30 times is shown in Table 1.Also listed in the table 1 not through coating the LiCoO of the high temperature solid-state method preparation of handling 2The Electrochemical results of sample.
The composition of table 1 electrode material and electrochemistry cycle performance
Figure A20081011209900041
Figure A20081011209900051
Characteristics of the present invention and advantage are: preparation FePO provided by the invention 4Coat LiCoO 2The method technology of combination electrode material is simple, with low cost, and coating layer is even, controllable thickness, suitability for scale production.Employing has the FePO of electro-chemical activity 4To LiCoO 2Carry out surface coating modification, make internal layer LiCoO 2Electrode material and electrolyte separate, and dissolving and electrolyte because of cobalt when having reduced high potential decompose the capacitance loss that causes; Again because FePO 4Can bear higher charging potential, so FePO 4The LiCoO that coats 2Composite positive pole has the specific capacity of better electrochemistry cycle performance and Geng Gao, improves when having taken into account material specific capacity and cycle performance.
Description of drawings:
Fig. 1 .FePO 4Coat LiCoO 2The XRD spectra of combination electrode material.
Abscissa is angle 2 θ, and unit is: degree (°);
Ordinate is a diffracted intensity, and unit is: absolute unit (a.u.).
Fig. 2. coat LiCoO with FePO4 2Composite material is anodal Experimental cell first charge-discharge curve (a is a charging curve, and b is a discharge curve), and its charging/discharging voltage scope is 2.75～4.5V.
Abscissa is a specific discharge capacity, and unit is: MAH/gram (mAh/g);
Ordinate is a voltage, and unit is: volt, and with respect to Li +/ Li electrode (V vs.Li +/ Li).
Fig. 3. with FePO 4Coat LiCoO 2Composite material is the cycle performance curve of the Experimental cell of positive pole, and its charging/discharging voltage scope is 2.75～4.5V.
Abscissa is a cycle-index, and unit is: inferior;
Ordinate is a specific discharge capacity, and unit is: MAH/gram (mAh/g).
Fig. 4. the LiCoO of uncoated processing 2The field emission scanning electron microscope photo of electrode material.
Interior illustration: the field emission scanning electron microscope photo under the high enlargement ratio.
Fig. 5. the FePO for preparing by embodiment 1 4Coat LiCoO 2The field emission scanning electron microscope photo of combination electrode material.
Interior illustration: the field emission scanning electron microscope photo under the high enlargement ratio.
Fig. 6. the FePO for preparing by embodiment 1 4Coat LiCoO 2The transmission electron microscope photo of combination electrode material
Embodiment:
Embodiment 1:
Take by weighing the LiCoO of 48.5g 2Fe (the NO of material and 4.05g 3) 39H 2O adds the 100mL deionized water, is mixed with Fe 3+Concentration is the suspension-turbid liquid of 0.1mol/L, is that 25 ℃, power are sonicated 30 minutes under the condition of 2000W/L in temperature, the slurries after ultrasonic is transferred in the there-necked flask continued mechanical agitation 1 hour, drips (the NH of 0.1mol/L then under mechanical agitation 4) 2HPO 4Solution 120mL, wherein n (PO 4 3-)/n (Fe 3+)=1.2/1 (mol ratio) dropwises the back and continues to stir 1 hour.After reaction finishes, filtering, is 7 with deionized water wash to filtrate pH value.Filter cake in 130 ℃ baking oven dry 6 hours grinds standby.
The powder body material that grinding is obtained is warming up to 550 ℃ with 5 ℃/min speed, and constant temperature 10 hours, naturally cools to room temperature then, obtains product of the present invention.
Adopt day island proper Tianjin ICPS-7500 type inductive coupling plasma emission spectrograph to measure metal ion Li in the product, Co, the content of Fe determines that it contains the FePO of 3wt.% in forming 4, all the other are LiCoO 2Adopt day island proper Tianjin XRD-6000 type x-ray powder diffraction instrument (Cu K αRadiation, λ=1.5406 ) characterize product structure, its XRD test result as shown in Figure 1, product belongs to hexagonal crystal system, has α-NaFeO 2The type layer structure does not have any impurity peaks, and FePO is described 4Coating is to LiCoO 2Body construction do not play any destruction; Electrochemical results sees Table 1, and (the charging/discharging voltage scope: 2.75～4.5V) see Fig. 2 to the first charge-discharge curve, and the cycle performance curve is seen Fig. 3, shows FePO 4Coat LiCoO 2Have good electrochemistry cyclical stability and anti-over-charging electrical property, and the reversible specific capacity loss is less; Adopt FDAC S-4700 field emission scanning electron microscope to characterize the LiCoO that does not coat 2Precursor and 3wt.%FePO 4The LiCoO that coats 2The pattern of composite material, test result are seen Fig. 4 and Fig. 5 respectively, show at composite material surface to have formed uniform coating layer; Adopt FDAC H-800 transmission electron microscope to characterize 3wt.%FePO 4The LiCoO that coats 2The thickness of composite material coating layer, test result is seen Fig. 6, its thickness is 150nm.
Embodiment 2:
Take by weighing the LiCoO of 74.5g 2Fe (the NO of material and 2.02g 3) 39H 2O adds the 100mL deionized water, is mixed with Fe 3+Concentration is the suspension-turbid liquid of 0.05mol/L, is that 20 ℃, power are sonicated 60 minutes under the condition of 800W/L in temperature, the slurries after ultrasonic is transferred in the there-necked flask continued mechanical agitation 1.5 hours, drips (the NH of 0.05mol/L then under mechanical agitation 4) 2HPO 4Solution 150mL, wherein n (PO 4 3-)/n (Fe 3+)=1.5/1 (mol ratio) dropwises the back and continues to stir 0.5 hour.After reaction finishes, filtering, is 7 with deionized water wash to filtrate pH value.Filter cake in 50 ℃ baking oven dry 12 hours grinds standby.
The powder body material that grinding is obtained is warming up to 350 ℃ with 2 ℃/min speed, and constant temperature 15 hours, naturally cools to room temperature then, obtains product of the present invention.ICP and XRD test shows product consist of 5wt.%FePO 4The LiCoO that coats 2Composite material belongs to hexagonal crystal system, and Electrochemical results sees Table 1.
Embodiment 3:
Take by weighing the LiCoO of 84.8g 2Fe (the NO of material and 12.12g 3) 39H 2O adds the 100mL deionized water, is mixed with Fe 3+Concentration is the suspension-turbid liquid of 0.3mol/L, is that 40 ℃, power are sonicated 45 minutes under the condition of 1000W/L in temperature, the slurries after ultrasonic is transferred in the there-necked flask continued mechanical agitation 30 minutes, drips (the NH of 0.3mol/L then under mechanical agitation 4) 2HPO 4Solution 100mL, wherein n (PO 4 3-)/n (Fe 3+)=1/1 (mol ratio) dropwises the back and continues to stir 1 hour.After reaction finishes, filtering, is 7 with deionized water wash to filtrate pH value.Filter cake in 120 ℃ baking oven dry 12 hours grinds standby.
The powder body material that grinding is obtained is warming up to 450 ℃ with 10 ℃/min speed, and constant temperature 10 hours, naturally cools to room temperature then, obtains product of the present invention.ICP and XRD test shows product consist of 1wt.%FePO 4The LiCoO that coats 2Composite material belongs to hexagonal crystal system, and Electrochemical results sees Table 1.
Embodiment 4:
Take by weighing the LiCoO of 48.5g 2Fe (the NO of material and 4.05g 3) 39H 2O adds the 100mL deionized water, is mixed with Fe 3+Concentration is the suspension-turbid liquid of 0.1mol/L, and sonicated is 60 minutes under 25 ℃ of temperature, power 1500W/L condition, the slurries after ultrasonic is transferred in the there-necked flask continued mechanical agitation 1 hour, drips (the NH of 0.45mol/L then under mechanical agitation 4) 2HPO 4Solution 34mL, wherein n (PO 4 3-)/n (Fe 3+)=1.5/1 (mol ratio) dropwises the back and continues to stir 1.5 hours.After reaction finishes, filtering, is 7.5 with deionized water wash to filtrate pH value.Filter cake in 150 ℃ baking oven dry 6 hours grinds standby.
The powder body material that grinding is obtained is warming up to 350 ℃ with 2 ℃/min speed, and constant temperature 15 hours, naturally cools to room temperature then, obtains product of the present invention.ICP and XRD test shows product consist of 3wt.%FePO 4The LiCoO that coats 2Composite material belongs to hexagonal crystal system, and Electrochemical results sees Table 1.
Embodiment 5:
Take by weighing the LiCoO of 56.56g 2Fe (the NO of material and 8.08g 3) 39H 2O adds the 100mL deionized water, is made into Fe 3+Concentration is the suspension-turbid liquid of 0.2mol/L, is that 20 ℃, power are sonicated 15 minutes under the condition of 2000W/L in temperature, the slurries after ultrasonic is transferred in the there-necked flask continued mechanical agitation 0.5 hour, drips (the NH of 0.45mol/L then under mechanical agitation 4) 2HPO 4Solution 53mL, wherein n (PO 4 3-)/n (Fe 3+)=1.2/1 (mol ratio) dropwises the back and continues to stir 1.5 hours.After reaction finishes, filtering, is 7.5 with deionized water wash to filtrate pH value.Filter cake in 130 ℃ baking oven dry 8 hours grinds standby.
The powder body material that grinding is obtained is warming up to 550 ℃ with 10 ℃/min speed, and constant temperature 5 hours, naturally cools to room temperature then, obtains product of the present invention.ICP and XRD test shows product consist of 1wt.%FePO 4The LiCoO that coats 2Composite material belongs to hexagonal crystal system, and Electrochemical results sees Table 1.

Claims (1)

1, a kind of preparation method of lithium cobaltate composite electrode material coated by iron phosphate is characterized in that, concrete processing step is as follows:
A, with LiCoO 2And Fe (NO 3) 39H 2O joins in the deionized water in 7: 1～37: 1 ratio of mass ratio, is made into Fe 3+Concentration be the suspension-turbid liquid of 0.05～0.3mol/L, and to control its pH value be 2.0～3.0; In temperature is 20～40 ℃, and power is sonicated 15～60 minutes under 800～2000W/L condition; Then suspension-turbid liquid is transferred in the there-necked flask, mechanical agitation 30～90 minutes drips the (NH of 0.05～0.45mol/L again under mechanical agitation 4) 2HPO 4Solution, wherein (NH 4) 2HPO 4With Fe (NO 3) 3Mol ratio be 1: 1～1.5: 1, continue to stir 30～90 minutes; The suspension-turbid liquid that obtains is filtered, and is 7～7.5 with the deionized water wash product to filtrate pH value, and filter cake is following dry 6～12 hours at 50～150 ℃;
B, steps A gained material is warming up to 350～550 ℃ with 2～10 ℃/min speed, and constant temperature 5～15 hours, naturally cool to room temperature then, obtain lithium cobaltate composite electrode material coated by iron phosphate.
CNB2008101120999A 2008-05-21 2008-05-21 A kind of preparation method of lithium cobaltate composite electrode material coated by iron phosphate Expired - Fee Related CN100565985C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2008101120999A CN100565985C (en) 2008-05-21 2008-05-21 A kind of preparation method of lithium cobaltate composite electrode material coated by iron phosphate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2008101120999A CN100565985C (en) 2008-05-21 2008-05-21 A kind of preparation method of lithium cobaltate composite electrode material coated by iron phosphate

Publications (2)

Publication Number Publication Date
CN101276913A true CN101276913A (en) 2008-10-01
CN100565985C CN100565985C (en) 2009-12-02

Family

ID=39996065

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2008101120999A Expired - Fee Related CN100565985C (en) 2008-05-21 2008-05-21 A kind of preparation method of lithium cobaltate composite electrode material coated by iron phosphate

Country Status (1)

Country Link
CN (1) CN100565985C (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101916848A (en) * 2010-08-06 2010-12-15 山东久力电子科技有限公司 LiFePO4 coating LiMn2O4 composite electrode material and preparation method thereof
CN101969110A (en) * 2010-08-31 2011-02-09 天津巴莫科技股份有限公司 Fast ion conductor modified lithium ion battery cathode material lithium cobalt oxide with fast ion conductor and preparation method
CN104692352A (en) * 2013-12-05 2015-06-10 中国电子科技集团公司第十八研究所 Method for surface coating of lithium ion battery anode material with nanoscale iron phosphate
CN105301194A (en) * 2015-10-30 2016-02-03 江苏华东锂电技术研究院有限公司 Detection method of surface covering effect of positive electrode active material
CN106654196A (en) * 2016-11-22 2017-05-10 深圳市沃特玛电池有限公司 Preparation method for ternary positive electrode material of lithium battery
CN111082031A (en) * 2020-01-09 2020-04-28 广东邦普循环科技有限公司 Preparation method of lithium phosphate coated high-nickel ternary cathode material
CN117125687A (en) * 2021-05-31 2023-11-28 福建师范大学 Method for circularly regenerating iron phosphate for lithium battery from positive lithium iron phosphate of waste lithium battery

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101916848A (en) * 2010-08-06 2010-12-15 山东久力电子科技有限公司 LiFePO4 coating LiMn2O4 composite electrode material and preparation method thereof
CN101969110A (en) * 2010-08-31 2011-02-09 天津巴莫科技股份有限公司 Fast ion conductor modified lithium ion battery cathode material lithium cobalt oxide with fast ion conductor and preparation method
CN104692352A (en) * 2013-12-05 2015-06-10 中国电子科技集团公司第十八研究所 Method for surface coating of lithium ion battery anode material with nanoscale iron phosphate
CN104692352B (en) * 2013-12-05 2018-05-11 中国电子科技集团公司第十八研究所 The method that anode material for lithium-ion batteries surface coats nanoscale iron phosphate
CN105301194A (en) * 2015-10-30 2016-02-03 江苏华东锂电技术研究院有限公司 Detection method of surface covering effect of positive electrode active material
CN105301194B (en) * 2015-10-30 2018-01-16 江苏华东锂电技术研究院有限公司 The detection method of surface of positive electrode active material covered effect
CN106654196A (en) * 2016-11-22 2017-05-10 深圳市沃特玛电池有限公司 Preparation method for ternary positive electrode material of lithium battery
CN111082031A (en) * 2020-01-09 2020-04-28 广东邦普循环科技有限公司 Preparation method of lithium phosphate coated high-nickel ternary cathode material
CN117125687A (en) * 2021-05-31 2023-11-28 福建师范大学 Method for circularly regenerating iron phosphate for lithium battery from positive lithium iron phosphate of waste lithium battery

Also Published As

Publication number Publication date
CN100565985C (en) 2009-12-02

Similar Documents

Publication Publication Date Title
Lavela et al. Sol–gel preparation of cobalt manganese mixed oxides for their use as electrode materials in lithium cells
KR102402147B1 (en) Manganese spinel doped with magnesium, cathode material comprising said manganese spinel, method for preparing the same, and lithium ion battery comprising said spinel
Liang et al. Co-doped Li4Ti5O12 nanosheets with enhanced rate performance for lithium-ion batteries
Alsamet et al. Synthesis and characterization of nano-sized LiFePO4 by using consecutive combination of sol-gel and hydrothermal methods
Thirunakaran et al. Electrochemical evaluation of dual-doped LiMn2O4 spinels synthesized via co-precipitation method as cathode material for lithium rechargeable batteries
CN114790013A (en) Sodium ion battery positive electrode active material capable of self-supplementing sodium, and preparation method and application thereof
CN100565985C (en) A kind of preparation method of lithium cobaltate composite electrode material coated by iron phosphate
KR101781764B1 (en) Alkali metal titanium oxide having anisotropic structure, titanium oxide, electrode active material containing said oxides, and electricity storage device
Shu et al. Magnesium and silicon co-doped LiNi0. 5Mn1. 5O4 cathode material with outstanding cycling stability for lithium-ion batteries
Hou et al. Drastic enhancement in the rate and cyclic behavior of LiMn2O4 electrodes at elevated temperatures by phosphorus doping
CN101826617B (en) Preparation method of lithium iron phosphate
CN101510606A (en) Composite metal oxide coating spinelle type LiMn2O4 anode material and preparation method
CN101315981A (en) Lithium iron phosphate anode material for lithium ion battery and modification method
Wu et al. Enhancing performances of Co-free Li-rich Mn-based layered cathode materials via interface modification of multiple-functional Mn3O4 shell
Thirunakaran et al. Studies on chromium/aluminium-doped manganese spinel as cathode materials for lithium-ion batteries—A novel chelated sol–gel synthesis
Chen et al. Facile preparation of carbon-LiNi1/3Co1/3Mn1/3O2 with enhanced stability and rate capability for lithium-ion batteries
Kurilenko et al. The effect of synthesis conditions on the morphology, cation disorder and electrochemical performance of Li1+ xNi0. 5Mn0. 5O2
JP5369447B2 (en) Lithium titanium iron composite oxide, method for using the same, lithium ion secondary battery, and method for producing lithium titanium iron composite oxide
Wang et al. Preparation and performance of Mg-doped spinel-structured LiMn2O4 cathode materials
Chchiyai et al. Synthesis and electrochemical properties of Mn-doped porous Mg0. 9Zn0. 1Fe2− xMnxO4 (0≤ x≤ 1.25) spinel oxides as anode materials for lithium-ion batteries
Yang et al. Improving the electrochemical performance of Li1. 2Mn0. 54Ni0. 13Co0. 13O2 cathode through sodium doping
Liu et al. Improving the electrochemical performance of single crystal LiNi0. 5Mn1. 5O4 cathode materials by Y–Ti doping and unannealing process
CN101847715A (en) Preparation method of spinel-type LiMn2O4 cathode material coated by cobalt-aluminum composite metal oxide
Murali et al. Preparation, dielectric and conductivity studies of LiNi1-xMgxO2 cathode materials for lithium-ion batteries
CN116639740A (en) Cobalt-free lithium-rich manganese-based positive electrode material and preparation method thereof

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
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20091202

Termination date: 20100521