CN102306776A - Method for preparing cathode material of lithium ion battery - Google Patents

Method for preparing cathode material of lithium ion battery Download PDF

Info

Publication number
CN102306776A
CN102306776A CN201110249813A CN201110249813A CN102306776A CN 102306776 A CN102306776 A CN 102306776A CN 201110249813 A CN201110249813 A CN 201110249813A CN 201110249813 A CN201110249813 A CN 201110249813A CN 102306776 A CN102306776 A CN 102306776A
Authority
CN
China
Prior art keywords
lithium
preparation
carbonate
source
transition metal
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.)
Pending
Application number
CN201110249813A
Other languages
Chinese (zh)
Inventor
周恒辉
谭卓
高平
成富圈
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.)
Xianxing Science-Technology-Industry Co Ltd Beijing Univ
Original Assignee
Xianxing Science-Technology-Industry Co Ltd Beijing Univ
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 Xianxing Science-Technology-Industry Co Ltd Beijing Univ filed Critical Xianxing Science-Technology-Industry Co Ltd Beijing Univ
Priority to CN201110249813A priority Critical patent/CN102306776A/en
Publication of CN102306776A publication Critical patent/CN102306776A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a method for preparing a cathode material of a lithium ion battery. The method comprises the following steps of: firstly, preparing solution by using soluble salt of more than two transition metals, adding the solution into carbonate solution and reacting to obtain a polynary transition metal carbonate precursor; secondly, adding the precursor, a lithium source and a phosphorus source into a liquid dispersion medium, and adding a carbon source; and finally, performing ball milling, uniformly mixing, drying, calcining, and thus obtaining the polynary metal ion doped olivine type cathode material of the lithium ion battery. The method has a simple process, is low in cost and is suitable for industrial application; polynary metal element atoms can be mixed in a horizontal level through homogeneous precipitation; and by controlling process conditions, the proportion of polynary metals and the particle size of a product can be effectively controlled. The prepared cathode material has the primary particle size of between 0.1 and 20 micrometers and has higher energy density, higher electrical performance and higher cycle performance.

Description

A kind of preparation method of anode material for lithium-ion batteries
Technical field
The invention belongs to technical field of lithium ion, be specifically related to obtain the preparation method of the olivine-type anode material for lithium-ion batteries of multiple metal ion doping through homogeneous precipitation method.
Background technology
Along with lithium ion battery in recent years is applied to the commercialization market of miniaturized electronics on a large scale as power supply; And the market demand that is faced with ever-increasing electric motor car and hybrid vehicle, have high-energy-density, good circulation performance, lithium ion battery material causes extensive concern cheaply.From reported first such as Goodenough in 1997 have an olivine-type LiFePO of better electrochemical activation 4Since the positive electrode, LiFePO4 (LiFePO 4) with the theoretical capacity of its 170mAh/g, raw material sources extensively, characteristics such as avirulence, excellent cycle performance and good safety performance receive extensive concern.Yet, because olivine-type LiFePO 4Belong to rhombic system, the distribution of oxygen atom is close to close heap hexagon, and the free volume that lithium ion moves is little, causes the ionic diffusion coefficient of said material and electron diffusion coefficient less, than other positive electrode such as layered oxide Li 1-xMO 2Much lower.Simultaneously, because LiFePO 4Less electron diffusion coefficient often will improve electron diffusion coefficient through adding good electronic conductors such as carbon in practical application, cause LiFePO 4The positive electrode tap density reduces, and energy density further reduces.The problems referred to above have become the bottleneck place of its development and application.
LiFePO 4Current potential with respect to lithium has only 3.4V, and has the LiMnPO of same structure 4The current potential of lithium is 4.1V relatively, so LiMnPO 4On theoretical energy density, compare LiFePO 4Exceed 30%.The manganese source is abundant simultaneously, and low price was also shown great attention in recent years.And LiFePO 4Compare, the introducing of Mn element can partly be brought up to 4.1V with the current potential that discharges and recharges of this positive electrode, thereby can improve the energy density of positive electrode to a great extent.But it is not at present still deep enough for the research of the relation between composition, structure and the performance thereof of polynary olivine-type positive electrode; And conventional high-energy ball milling method can not effectively make multiple metal ion in material, be uniformly dispersed, and sol-gal process and microwave rule energy consumption are big, and the time cycle is long, and is also quite high to the requirement of equipment simultaneously, is difficult to overcome these difficulties in present stage.
Summary of the invention
The present invention provides a kind of low cost for solving above-mentioned existing in prior technology problem, and is applicable to the preparation method of the carbonate series multiple metal ion doping olivine-type anode material for lithium-ion batteries of industrial applications.
The chemical composition of anode material for lithium-ion batteries of the present invention is LiMPO 4/ C compound, wherein M represents the combination of two or more transition metals, and its preparation method may further comprise the steps:
(1) soluble-salt of two or more transition metal is formulated as solution and joins in the carbonate solution, in closed reaction vessel, regulating the pH value is 4.0~7.0, and control reaction temperature is 30~90 ℃; Reaction 1h~20h; Washing is then filtered, and obtains polynary transition metal carbonate precursor;
(2) lithium source, phosphorus source and polynary transition metal carbonate precursor are joined in the liquid dispersion medium; And interpolation carbon source; Ball mill mixing 5~12h; Solid-liquid is mixed mutually; Then that mixture is dry; Protect following 300 ℃~800 ℃ once or several times to calcine 5h~25h in inertia or reducing atmosphere, obtain the olivine-type anode material for lithium-ion batteries.
Among the above-mentioned preparation method, said transition metal is preferably Fe, Mn, Ni and Co, with two or more collocation formation LiMPO wherein 4M in the/C compound.Preferred, M is one of following binary or the combination of three element/transition metals: Fe+Mn, Fe+Ni, Fe+Co, Fe+Ni+Co, Fe+Ni+Mn, Fe+Mn+Co, Mn+Ni, Mn+Co, Mn+Ni+Co or Ni+Co.
In the step (1), the soluble-salt of said transition metal is preferably the sulfate of said transition metal, nitrate, acetate or chloride; Said carbonate can be selected ammonium carbonate, carbonic hydroammonium, sodium acid carbonate or sodium carbonate.Usually the soluble-salt of two or more transition metal is mixed with the solution of 0.1~4mol/L, this solution is joined in 0.1~3mol/L carbonate solution in proportion react again.With the ammonia spirit of 2.0~8.0mol/L, the sodium hydroxide solution of 0.5~2mol/L and/or the inorganic acid solution conditioned reaction pH of 0.5~2mol/L.
In the step (2), said lithium source is preferably one or more in lithium carbonate, lithium dihydrogen phosphate, lithium hydroxide, lithium oxalate, lithium chloride, lithium sulfate and the lithium citrate; Said phosphorus source refers to contain the compound of phosphate radical, is preferably in phosphoric acid, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, ammonium phosphate, lithium phosphate, diammonium hydrogen phosphate and the sodium hydrogen phosphate one or more; Said liquid dispersion medium is water or organic solvent, and said organic solvent can be one or more in ethanol, acetone, propyl alcohol, ethylene glycol, the ethylenediamine.Lithium source and phosphorus source can be with a kind of compound, for example lithium dihydrogen phosphate.With lithium source, phosphorus source and polynary transition metal carbonate precursor by Li: P: the M mol ratio is (1~1.05): (0.9~1): (0.85~1) joins in the liquid dispersion medium; And the interpolation carbon source, the addition of carbon source is counted 1~20% of lithium source, phosphorus source and polynary transition metal carbonate precursor gross mass by quality.Said carbon source can be one or more in acetylene black, graphite, citric acid, ascorbic acid, sucrose, glucose, cellulose and the phenolic resins.
In the step (2), inertia or reducibility gas can be a kind of in nitrogen, helium, argon gas, hydrogen or the argon hydrogen mixture.
Characteristics of the present invention and advantage are:
The method of the carbonate series multiple metal ion doping olivine-type anode material for lithium-ion batteries of the present invention preparation, have with low cost, synthesis technique is simple and the characteristics of suitable industrial applications.Realize the mixing of multi-metal element atomic level level through precipitation from homogeneous solution; Through to control of process condition, control the granularity of ratio and product between multi-element metal effectively.
The carbonate series multiple metal ion doping olivine-type anode material for lithium-ion batteries of the present invention's preparation; The primary particle particle diameter is at 0.1 μ m~20 μ m; Under the room temperature; 0.1C rate charge-discharge, discharge capacity can reach 155mAh/g first, and two or more charge and discharge platform are arranged; The intermediate value current potential is at 3.5~4.5V; Improve the energy density of olivine-type anode material for lithium-ion batteries significantly, can keep the good electrical properties cycle performance simultaneously, had commercial application prospect.
Description of drawings
Fig. 1 is the sem photograph of the prepared binary ferrimanganic carbonate precursor of embodiment 1.
Fig. 2 is the X-ray diffraction spectrogram of the prepared binary ferrimanganic carbonate precursor of embodiment 1.
Fig. 3 is the prepared LiFe of embodiment 2 0.6Mn 0.4PO 4The first charge-discharge curve chart of/C positive electrode.
Fig. 4 is the prepared LiFe of embodiment 2 0.6Mn 0.4PO 4The charge and discharge cycles Capacity Plan of/C positive electrode.
Fig. 5 is the prepared LiFe of embodiment 2 0.6Mn 0.4PO 4The cyclic voltammogram of/C positive electrode.
Fig. 6 is the prepared LiFe of embodiment 3 0.6Mn 0.4PO 4The sem photograph of/C positive electrode.
Embodiment
Embodiment 1
Fe+Mn (mol ratio of Fe: Mn is 0.6: 0.4) the mixed sulfate solution of 4L 0.5mol/L is mixed with the sal volatile of 2.5L 0.8mol/L, and control reaction temperature is 40 ℃, and pH is 6.0, prepares binary ferrimanganic carbonate precursor.To prepare precursor and lithium acetate, ammonium dihydrogen phosphate according to stoichiometric proportion (Fe+Mn): Li: P=0.92: mix at 1.03: 0.95; The sucrose that adds precursor and lithium acetate, ammonium dihydrogen phosphate gross mass 3% is as carbon source; With ethanol is liquid medium; Dry behind the ball mill mixing 6h, sieve, place airtight high-temperature service; Under the nitrogen atmosphere; In 400 ℃ of insulation 5h, be warming up to 650 ℃ of insulation 10h, be cooled to room temperature and obtain binary olivine-type LiFe 0.6Mn 0.4PO 4/ C positive electrode.
Fig. 1 is ESEM (SEM) figure of the binary ferrimanganic carbonate precursor of present embodiment preparation; Fig. 2 is binary ferrimanganic carbonate precursor X-ray diffraction (XRD) spectrogram; Compare with the standard spectrogram, can prove in the material of preparation does not have dephasign, is the pure phase of carbonic acid ferrimanganic.
Embodiment 2
Fe+Mn (mol ratio of Fe: Mn is 0.6: 0.4) the mixed sulfate solution of 4L 0.5mol/L is mixed with the sal volatile of 2.5L 0.8mol/L, and control reaction temperature is 40 ℃, and pH is 6.0, prepares binary ferrimanganic carbonate precursor.To prepare precursor and lithium acetate, ammonium dihydrogen phosphate according to stoichiometric proportion (Fe+Mn): Li: P=1: mix at 1: 1; The sucrose that adds precursor and lithium acetate, ammonium dihydrogen phosphate gross mass 3% mass fraction is as carbon source; With ethanol is liquid medium; Dry behind the ball mill mixing 6h; Sieve, place airtight high-temperature service, under the nitrogen atmosphere; Be warming up to 700 ℃ of insulation 10h, be cooled to room temperature and obtain binary olivine-type LiFe 0.6Mn 0.4PO 4/ C positive electrode.
Fig. 3 is the LiFe of present embodiment preparation 0.6Mn 0.4PO 4The first charge-discharge curve of/C positive electrode, as can be seen from Figure 3, this material has two charge and discharge platform, and the charge and discharge platform of 4.0~4.1V has improved the energy density of material.Fig. 4 is LiFe prepared in the present embodiment 0.6Mn 0.4PO 4The charge and discharge cycles Capacity Plan of/C positive electrode.Fig. 5 is LiFe prepared in the present embodiment 0.6Mn 0.4PO 4The cyclic voltammogram of/C positive electrode.
Embodiment 3
Fe+Mn (mol ratio of Fe: Mn is 0.6: 0.4) the mixed sulfate solution of 4L 0.5mol/L is mixed with the ammonium bicarbonate soln of 2.5L 0.8mol/L, and control reaction temperature is 60 ℃, and pH is 6.0, prepares binary ferrimanganic carbonate precursor.To prepare precursor and lithium acetate, ammonium dihydrogen phosphate according to stoichiometric proportion (Fe+Mn): Li: P=1: mix at 1: 1; The sucrose that adds precursor and lithium acetate, ammonium dihydrogen phosphate gross mass 2% mass fraction is as carbon source; With ethanol is liquid medium; Dry behind the ball mill mixing 6h; Sieve, place airtight high-temperature service, under the nitrogen atmosphere; Be warming up to 700 ℃ of insulation 10h, be cooled to room temperature and obtain binary olivine-type LiFe 0.6Mn 0.4PO 4/ C positive electrode.Fig. 6 is LiFe prepared in the present embodiment 0.6Mn 0.4PO 4The sem photograph of/C positive electrode.
Embodiment 4
Fe+Mn (mol ratio of Fe: Mn is 0.3: 0.7) the mixed sulfate solution of 4L 0.5mol/L is mixed with the sal volatile of 2.5L 0.8mol/L, and control reaction temperature is 40 ℃, and pH is 6.0, prepares binary ferrimanganic carbonate precursor.To prepare precursor and lithium carbonate, ammonium dihydrogen phosphate according to stoichiometric proportion (Fe+Mn): Li: P=1: mix at 1: 1; The glucose that adds precursor and lithium carbonate, ammonium dihydrogen phosphate gross mass 3% mass fraction is as carbon source; With ethanol is liquid medium; Dry behind the ball mill mixing 6h, sieve, place airtight high-temperature service; Under the nitrogen atmosphere; In 400 ℃ of insulation 5h, be warming up to 600 ℃ of insulation 10h, be cooled to room temperature and obtain binary olivine-type LiFe 0.3Mn 0.7PO 4/ C positive electrode.
Embodiment 5
Fe+Mn+Co (mol ratio of Fe: Mn: Co is 0.6: 0.3: 0.1) the mixed sulfate solution of 4L 0.5mol/L is mixed with the ammonium bicarbonate soln of 2.62L0.8mol/L; Control reaction temperature is 60 ℃; PH is 6.0, obtains celadon ternary ferrimanganic cobalt carbonate presoma.To prepare precursor and lithium carbonate, ammonium dihydrogen phosphate according to stoichiometric proportion (Fe+Mn+Co): Li: P=1: mix at 1: 1; The citric acid that adds precursor and lithium carbonate, ammonium dihydrogen phosphate gross mass 1% mass fraction is as carbon source; With acetone is liquid medium; Drying and screening behind the ball mill mixing 10h; Place airtight high-temperature service directly to be warming up to 700 ℃ of insulation 15h, be cooled to room temperature and obtain ternary olivine-type LiFe 0.6Mn 0.3Co 0.1PO 4/ C positive electrode.
Embodiment 6
Fe+Mn+Co (mol ratio of Fe: Mn: Co is 0.4: 0.3: 0.3) the mixed sulfate solution of 2.4L 1.5mol/L is mixed with the ammonium bicarbonate soln of 2L 1.8mol/L; Control reaction temperature is 60 ℃; PH is 6.5, obtains ternary ferrimanganic cobalt carbonate presoma.To prepare precursor and lithium carbonate; Ammonium dihydrogen phosphate is according to stoichiometric proportion (Fe+Mn+Co): Li: P=1: mix at 1: 1; The citric acid that adds precursor and lithium carbonate, ammonium dihydrogen phosphate gross mass 1% mass fraction is as carbon source; With acetone is liquid medium; Drying and screening behind the ball mill mixing 10h; Place airtight high-temperature service directly to be warming up to 700 ℃ of insulation 15h, be cooled to room temperature and obtain ternary olivine-type LiFe 0.4Mn 0.3Co 0.3PO 4/ C positive electrode.

Claims (10)

1. the preparation method of an anode material for lithium-ion batteries, said positive electrode is LiMPO 4/ C compound, wherein M represents the combination of two or more transition metals, and this preparation method may further comprise the steps:
1) soluble-salt of two or more transition metal is formulated as solution and joins in the carbonate solution, in closed reaction vessel, regulating the pH value is 4.0~7.0, and control reaction temperature is 30~90 ℃; Reaction 1h~20h; Washing is then filtered, and obtains polynary transition metal carbonate precursor;
2) lithium source, phosphorus source and polynary transition metal carbonate precursor are joined in the liquid dispersion medium; And interpolation carbon source; Ball mill mixing 5~12h; Solid-liquid is mixed mutually; Then that mixture is dry; Protect following 300 ℃~800 ℃ once or several times to calcine 5h~25h in inertia or reducing atmosphere, obtain the olivine-type anode material for lithium-ion batteries.
2. preparation method as claimed in claim 1 is characterized in that, the M representative is selected from the combination of the two or more transition metals among Fe, Mn, Ni and the Co.
3. preparation method as claimed in claim 2 is characterized in that, M is one of following binary or the combination of three element/transition metals: Fe+Mn, Fe+Ni, Fe+Co, Fe+Ni+Co, Fe+Ni+Mn, Fe+Mn+Co, Mn+Ni, Mn+Co, Mn+Ni+Co or Ni+Co.
4. preparation method as claimed in claim 1 is characterized in that, the soluble-salt of transition metal described in the step 1) is sulfate, nitrate, acetate or the chloride of transition metal; Said carbonate is ammonium carbonate, carbonic hydroammonium, sodium acid carbonate or sodium carbonate.
5. preparation method as claimed in claim 1 is characterized in that, step 1) is mixed with the solution of 0.1~4mol/L with the soluble-salt of two or more transition metal, this solution is joined in 0.1~3mol/L carbonate solution react again.
6. preparation method as claimed in claim 1 is characterized in that step 2) described in the lithium source be selected from lithium carbonate, lithium dihydrogen phosphate, lithium hydroxide, lithium oxalate, lithium chloride, lithium sulfate and the lithium citrate one or more.
7. preparation method as claimed in claim 1 is characterized in that step 2) described in the phosphorus source be selected from phosphoric acid, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, ammonium phosphate, lithium phosphate, diammonium hydrogen phosphate and the sodium hydrogen phosphate one or more.
8. preparation method as claimed in claim 1 is characterized in that step 2) in lithium source, phosphorus source and polynary transition metal carbonate precursor by Li: P: the M mol ratio is (1~1.05): (0.9~1): (0.85~1) joins in the liquid dispersion medium.
9. preparation method as claimed in claim 1 is characterized in that step 2) described in carbon source addition by quality count lithium source, phosphorus source and polynary transition metal carbonate precursor gross mass 1~20%.
10. preparation method as claimed in claim 1 is characterized in that step 2) described in carbon source be selected from acetylene black, graphite, citric acid, ascorbic acid, sucrose, glucose, cellulose and the phenolic resins one or more.
CN201110249813A 2011-08-26 2011-08-26 Method for preparing cathode material of lithium ion battery Pending CN102306776A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110249813A CN102306776A (en) 2011-08-26 2011-08-26 Method for preparing cathode material of lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110249813A CN102306776A (en) 2011-08-26 2011-08-26 Method for preparing cathode material of lithium ion battery

Publications (1)

Publication Number Publication Date
CN102306776A true CN102306776A (en) 2012-01-04

Family

ID=45380606

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110249813A Pending CN102306776A (en) 2011-08-26 2011-08-26 Method for preparing cathode material of lithium ion battery

Country Status (1)

Country Link
CN (1) CN102306776A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102593443A (en) * 2012-03-07 2012-07-18 浙江瓦力新能源科技有限公司 Method for preparing cathode activated nanometer composite material
CN103268938A (en) * 2013-01-22 2013-08-28 合肥国轩高科动力能源股份公司 Method for preparing lithium manganese iron phosphate solid solution lithium-ion cathode material
TWI464948B (en) * 2012-07-09 2014-12-11 Lg Chemical Ltd Precursor for preparing lithium composite transition metal oxide, method for preparing the precursor, and lithium composite transition metal oxide
CN104752719A (en) * 2013-12-27 2015-07-01 比亚迪股份有限公司 LiMnxFe1-xPO4 positive electrode active material and preparation method thereof
CN104852037A (en) * 2014-02-18 2015-08-19 北京有色金属研究总院 Precursor rich in iron on surface and rich in manganese on core and method for preparing carbon-coated manganese-iron-lithium phosphate material by taking precursor as raw material
CN110914194A (en) * 2017-07-19 2020-03-24 纳诺万材料公司 Improved synthesis of olivine-type lithium metal phosphate positive electrode materials
CN112811406A (en) * 2021-01-11 2021-05-18 天津市捷威动力工业有限公司 Biosynthesis method of high-performance olivine type manganese-based phosphate positive electrode material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101049922A (en) * 2007-05-18 2007-10-10 中南大学 Method for preparing anode material of lithium ion battery in series of phosphate of olivine type
CN101148264A (en) * 2006-09-19 2008-03-26 比亚迪股份有限公司 Method for preparing lithium ion battery positive electrode active material lithium-nickel-cobalt-oxygen
CN101645504A (en) * 2008-08-07 2010-02-10 赵兵 Method for preparing lithium iron phosphate of anode material of lithium ion battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101148264A (en) * 2006-09-19 2008-03-26 比亚迪股份有限公司 Method for preparing lithium ion battery positive electrode active material lithium-nickel-cobalt-oxygen
CN101049922A (en) * 2007-05-18 2007-10-10 中南大学 Method for preparing anode material of lithium ion battery in series of phosphate of olivine type
CN101645504A (en) * 2008-08-07 2010-02-10 赵兵 Method for preparing lithium iron phosphate of anode material of lithium ion battery

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102593443A (en) * 2012-03-07 2012-07-18 浙江瓦力新能源科技有限公司 Method for preparing cathode activated nanometer composite material
TWI464948B (en) * 2012-07-09 2014-12-11 Lg Chemical Ltd Precursor for preparing lithium composite transition metal oxide, method for preparing the precursor, and lithium composite transition metal oxide
US9966600B2 (en) 2012-07-09 2018-05-08 Lg Chem, Ltd. Precursor for preparing lithium composite transition metal oxide, method for preparing the precursor, and lithium composite transition metal oxide
CN103268938A (en) * 2013-01-22 2013-08-28 合肥国轩高科动力能源股份公司 Method for preparing lithium manganese iron phosphate solid solution lithium-ion cathode material
CN104752719A (en) * 2013-12-27 2015-07-01 比亚迪股份有限公司 LiMnxFe1-xPO4 positive electrode active material and preparation method thereof
CN104752719B (en) * 2013-12-27 2017-10-13 比亚迪股份有限公司 A kind of LiMnxFe1‑xPO4Positive electrode active materials and preparation method thereof
CN104852037A (en) * 2014-02-18 2015-08-19 北京有色金属研究总院 Precursor rich in iron on surface and rich in manganese on core and method for preparing carbon-coated manganese-iron-lithium phosphate material by taking precursor as raw material
CN104852037B (en) * 2014-02-18 2017-08-04 北京有色金属研究总院 A kind of rich iron in surface, the presoma of the rich manganese of core and the method that carbon coating iron manganese phosphate lithium material is prepared by raw material of the presoma
CN110914194A (en) * 2017-07-19 2020-03-24 纳诺万材料公司 Improved synthesis of olivine-type lithium metal phosphate positive electrode materials
CN112811406A (en) * 2021-01-11 2021-05-18 天津市捷威动力工业有限公司 Biosynthesis method of high-performance olivine type manganese-based phosphate positive electrode material

Similar Documents

Publication Publication Date Title
CN101740752B (en) Core-shell composite anode material for lithium ion battery and preparation method thereof
CN103515594B (en) Lithium manganese phosphate/LiFePO4 Core-shell structure material that carbon is coated and preparation method thereof
JP5426654B2 (en) Method for preparing an iron source for preparing lithium iron phosphate and method for preparing lithium iron phosphate
US20230322557A1 (en) Method for preparing lithium manganese iron phosphate, cathode material, and lithium-ion battery
CN103794773B (en) A kind of method of producing high power capacity 523 type tertiary cathode material
CN102623708A (en) Preparation method of lithium vanadium phosphate (Li3V2(PO4)3)/graphene composite material for positive electrode of lithium ion battery
CN101237043A (en) Method for making ferrous lithium phosphate/carbon compound material of high active disorderly ferric phosphate
CN102306776A (en) Method for preparing cathode material of lithium ion battery
CN102427131A (en) Preparation method for metal magnesium-doped lithium manganese phosphate/carbon cathode material of lithium ion battery
CN103078113A (en) Vanadium-titanium ion-codoped lithium iron phosphate material and preparation method thereof
CN103985871A (en) Preparation method for positive electrode material of iron, lithium and manganese phosphate battery
CN101262060B (en) A method for making anode material Li3V2(PO4)3 of lithium ion battery
CN102110811B (en) Method for preparing nanoscale lithium ion battery LiFePo4/C anodal material
CN103000893A (en) Method for preparing lithium manganese phosphate positive material of lithium battery by spray pyrolysis
CN103996852A (en) Preparation method of novel nano lithium vanadium phosphate positive electrode material
CN103413944A (en) Lithium manganese phosphate positive electrode material and preparation method thereof
CN102738463A (en) Surface coating modification method of lithium vanadium phosphate cathode material by use of EDTA as carbon source
CN104868110A (en) Graphene-oriented mesoporous Co2V2O7 nanosheet material and production method and application thereof
CN100490221C (en) Composite doped modified lithium-ion battery anode material and its manufacture method
CN104752697A (en) Mixed ion phosphate positive electrode material and preparation method thereof
CN115863631A (en) Phosphate anode material and preparation method and application thereof
CN110085854B (en) Lithium vanadium phosphate cathode material and preparation method thereof
CN101262059B (en) A method for making anode material LiFePO4 of lithium ion battery
CN102945953A (en) Novel preparation method of high temperature-type long-life lithium ion battery anode material LiMn2-x-yMIxMIIyO4
CN108321390B (en) Three-dimensional flower-shaped single crystal lithium iron phosphate 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
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20120104