CN100490221C - Composite doped modified lithium-ion battery anode material and its manufacture method - Google Patents

Composite doped modified lithium-ion battery anode material and its manufacture method Download PDF

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CN100490221C
CN100490221C CNB2006101237861A CN200610123786A CN100490221C CN 100490221 C CN100490221 C CN 100490221C CN B2006101237861 A CNB2006101237861 A CN B2006101237861A CN 200610123786 A CN200610123786 A CN 200610123786A CN 100490221 C CN100490221 C CN 100490221C
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ion battery
anode material
battery anode
lithium
doping modification
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CN1964105A (en
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周震涛
谢辉
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South China University of Technology SCUT
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    • 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

Abstract

The disclosed preparation method for anode material of composite doped modified Li-ion cell comprises: mixing the Li-source compound, P-source compound, Fe-source compound, crystal phase doped M (rare earth element) compound and non-crystal phase doped element C to heat for 5-20h at 250-400Deg; cooling, and grinding to obtain the reaction predecessor contained PO43-, Li+, Mn+, Fe2+ and carbon black; calcining for 10-40h at 500-800Deg to cool and obtain the final product. This invention improves material electrochemical property and fit to industrial production.

Description

A kind of composite doping modification lithium-ion battery anode material and preparation method thereof
Technical field
The present invention relates to technical field of chemical power, specifically be meant a kind of composite doping modification lithium-ion battery anode material and preparation method thereof.
Background technology
LiFePO4 (LiFePO 4) be a kind of anode material for lithium-ion batteries of olivine-type crystalline structure, have charging and discharging capacity big, have extended cycle life, outstanding advantages such as security performance is good, inexpensive, nontoxic pollution-free, be considered to the LiCoO that continues 2, LiNiO 2, LiMn 2O 4The anode material for lithium-ion batteries that development potentiality is arranged most afterwards is with a wide range of applications.
Yet LiFePO4 yet exists some significant disadvantage, mainly is that the migration rate and the electron conductivity of its lithium ion is all lower, and charge and discharge process is subjected to Li +At LiFePO 4-FePO 4Diffusion velocity between the two-phase is controlled, and its grain growth level is wayward when synthetic, thereby has greatly limited its practical application.Therefore, research up to now mainly is to concentrate on to improve its ionic conductivity and two aspects of electronic conductivity: be the growth by material grains in the control material building-up process on the one hand, obtain tiny and material homogeneous grain diameter, thereby reduce lithium ion migration path therein, reach the purpose that improves the lithium ion migration rate; Be the method for in building-up process, mixing on the other hand, introduce other metal heteroatom at crystals, improve the electronic conductivity of material in the method that intergranule is introduced conductive agent (as conductive carbon black) or adopted crystalline phase to mix by amorphous phase.As people [Electrochemistry Communications such as Yang Shou feng, 505~508 (3), 2001] people [Electrochemistry Communnications such as the hydrothermal synthesis method of Cai Yonging, Park, 839~842 (5), 2003] people [Electrochemical and Solid State Letters such as the liquid-phase coprecipitation of Cai Yonging, Croce F, A47~A50 (5), 2002] sol-gel processing of Cai Yonging etc., synthesize granularity respectively than homogeneous, tiny LiFePO 4 material, improved the chemical property of material.G.Li and A.Yamada[JapanPat.WO 00/60679 (2000)] reported at preparation LiFePO 4The time synthesize LiFePO with the method for adding carbon black 4/ C composite material, thus the electric conductivity of this material improved; People such as F.Croce [Electrochemical and Solid State Letters 5 (3), 2002] have reported at synthetic LiFePO 4The time come the electron conduction of reinforcing material with the method for direct doping metals copper or silver powder; And people such as AtsuoYamada [Journal of The Electrochemical Society, 148 (8), 2001] then synthesize Li (Mn by the method for containing transition metal element manganese yFe 1-y) PO 4, improve the chemical property of material.Though its chemical property has some improvement, also there is following problems in ferric phosphate (II) lithium composite material with said method synthesized:
Though 1, adopt synthetic methods such as hydrothermal synthesis method, liquid-phase coprecipitation, sol-gel processing can synthesize granularity than homogeneous, LiFePO that particle diameter is more tiny 4The material powder has shortened Li +The evolving path, but not obvious, and said method also exists equipment requirements height or technology than shortcomings such as complexity, is difficult for carrying out industrialization production to the improvement of material electric conductivity.
2, adopt the method for simple doping carbon, the carbon black consumption is more, because the density of carbon black compares LiFePO 4Much smaller, thereby can reduce the real density of material significantly, thereby also reduced the volumetric specific energy and the volumetric specific power of material;
3, directly the metal dust sedimentation easily takes place in the technical process of doping metals powder method, and a top-down concentration gradient appears in metal dust, makes metal dust at LiFePO 4Skewness in the material, thus the electrical property of material influenced;
4, containing transition metal (M) Li (Mn that element such as manganese or cobalt etc. generated yFe 1-y) PO 4, the material crystals stability of structure is reduced, thereby also influence the electrical property of material.
Summary of the invention
Purpose of the present invention is exactly in order to solve above-mentioned the deficiencies in the prior art part, and a kind of composite doping modification lithium-ion battery anode material and preparation method thereof is provided.The present invention is that crystalline phase is a dopant with rare earth element M such as La, Y, Nd, Ce, adopt the method for amorphous phase-crystalline phase codope, come the synthesis modification positive electrode by high temperature solid state reaction, can control the size of chemical composition, structure and the grain diameter of composite doping modification positive electrode effectively, improve the electronic conductivity and the lithium ion diffusion rate of material, improve the chemical property of material; Simultaneously also simplify material synthesis, be convenient to carry out industrialized production..
Purpose of the present invention realizes by following technical solution: the preparation method of described a kind of composite doping modification lithium-ion battery anode material comprises the steps and process conditions:
The first step is with the compound of compound and the amorphous phase doped chemical C of Li source compound, P source compound, Fe source compound, crystalline phase doped with rare-earth elements M, wherein the mol ratio of Li: Fe: P: M is 1: (0.97~0.995): 1: (0.005~0.03), and the addition of the compound of amorphous phase doped chemical C is 1~10wt% of mixture gross mass;
Second step heated mixed raw material 5~20 hours down at 250~400 ℃, obtained containing PO after cooling, the grinding 4 3-, Li +, M N+, Fe 2+Reaction precursor body with carbon black;
The 3rd step calcined the reaction precursor body 10~40 hours down at 500~800 ℃, promptly got LiFe after the cooling (1-x)M xPO 4The anode material for lithium-ion batteries of/C composite doping modification.
In order to realize the present invention better, described Li source compound is one or more mixtures in lithium nitrate, lithium carbonate, the lithium acetate; Described P source compound is one or more mixtures in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, the diammonium hydrogen phosphate; Described Fe source compound is a kind of or their mixture in ferrous oxalate, the ferrous acetate; The compound of described crystalline phase doped with rare-earth elements M is one or more mixtures in lanthanum acetate, acetic acid yttrium, acetic acid neodymium, the cerous acetate; The compound of described amorphous phase doped chemical C is one or more mixtures in glucose, epoxy resin, cellobiose, the cyclodextrin; The described first step is to be dispersant with ethanol, and the addition of ethanol is 40~60wt% of mixture gross mass, through the high speed ball milling raw material is mixed and is uniformly dispersed; Described second step is that mixed raw material is put into pit-type furnace, feeds the protection of nitrogen do and adds thermal response; Described the 3rd step is that the presoma of reaction is put into reactor, places pit-type furnace, feeds nitrogen do protection carrying out calcination reaction.
A kind of composite doping modification lithium-ion battery anode material of the present invention forms by method for preparing exactly.
The present invention compared with prior art has following advantage and beneficial effect:
1, the LiFe of the present invention's preparation (1-x)M xPO 4The crystal structure of/C composite doping modification positive electrode and pure LiFePO 4Crystal structure basic identical;
2, the LiFe for preparing in the present invention (1-x)M xPO 4In the crystal structure of/C composite doping modification positive electrode, rare earth elemental metals ion (M N+) (M=La, Y, Nd, Ce) enter the inside of positive electrode crystal structure, improved LiFePO in the charge and discharge process 4/ FePO 4State of interface, strengthened the ionic conducting property and the electronic conductivity of material, thereby helped Li +Embedding and deviate from; And be evenly distributed on LiFe (1-x)M xPO 4The nano grade carbon black of/C intergranule has then strengthened the electronic conductivity of material, simultaneously, this nano grade carbon black can also suppress the growth of crystal effectively as the matrix that forms the composite ferric lithium phosphate material crystal, improve the ionic conducting property of material, thereby make LiFe (1-x)M xPO 4The electrical property of/C composite positive pole has obtained significant raising;
3, since the consumption of doping element compound of the present invention seldom, gained LiFe (1-x)M xPO 4Change very for a short time before and after the real density of/C composite positive pole, therefore adopt technical scheme of the present invention all very little the influence of the volumetric specific energy of gained material and volumetric specific power.
4, the LiFe of the present invention's preparation (1-x)M xPO 4The superior performance of the embedding of/C composite positive pole, lithium ionic insertion/deinsertion has higher specific discharge capacity and excellent charging and discharging cycle performance.At room temperature, when 2.8~4.3V, its first discharge specific capacity reaches 159.4mAh/g to this material, is 93.7% of theoretical specific capacity with 0.2C rate charge-discharge voltage range; Specific discharge capacity after 100 charge and discharge cycles is 156.2mAh/g, and capability retention is 98.0%.
5, the LiFe of the present invention's preparation (1-x)M xPO 4The high rate during charging-discharging of/C composite positive pole is good.At room temperature, during with 1.0C, 5.0C rate charge-discharge, its first discharge specific capacity is respectively 152.6mAh/g, 124.8mAh/g.
6, material synthesis of the present invention is simpler, is convenient to carry out industrialized production.
Description of drawings
Fig. 1 is the prepared LiFe of embodiment two 0.99La 0.01PO 4The X-ray diffracting spectrum of/C;
Fig. 2 is the prepared LiFe of embodiment two 0.99La 0.01PO 4/ C is assembled into the first charge-discharge curve behind the Experimental cell, and the charging/discharging voltage scope is 2.8~4.3V, and electrolyte is 1mol/LLiPF 6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1), charge-discharge magnification is 0.2C;
Fig. 3 is the prepared LiFe of embodiment two 0.99La 0.01PO 4/ C is assembled into the discharge curve of the circulation of rate charge-discharge first behind the Experimental cell, and the charging/discharging voltage scope is 2.8~4.3V, and electrolyte is 1mol/LLiPF 6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1), charge-discharge magnification is respectively 1.0C, 5.0C.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment one
The first step is mixed 1mol lithium nitrate, 1mol phosphoric acid, 0.995mol ferrous acetate, 0.005mol acetic acid yttrium and 36.0g glucose, is dispersant with 144.0g ethanol, mixes through the high speed ball milling;
Second step placed pit-type furnace with mixed raw material, fed nitrogen and protected, and heated 20 hours down at 250 ℃, must contain PO after cooling off, grinding 4 3-, Li +, Y 2+, Fe 2+Reaction precursor body with carbon black;
The 3rd step was put into reactor with the reaction precursor body, placed pit-type furnace, fed nitrogen and protected, and calcined 10 hours down at 500 ℃, with promptly getting LiFe after the stove cooling 0.995Y 0.005PO 4/ C composite doping modification positive electrode.
Adopt above-mentioned composite doping modification positive electrode to make cathode film as positive active material, cathode film consist of m Active material: m Acetylene black: m Ptfe emulsion (solid content)=80: 15: 5, thickness≤0.1mm made positive plate with the cathode film roll extrusion on stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard2300); Electrolyte is 1mol/LLiPF 6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas, at room temperature carry out charge-discharge test, and the charging/discharging voltage scope is 2.8~4.3V.When this material discharged and recharged with the 0.2C multiplying power, its first discharge specific capacity reached 146.4mAh/g; Specific discharge capacity after 100 charge and discharge cycles is 138.2mAh/g, and capability retention is 94.4%; During with 1.0C, 5.0C rate charge-discharge, its first discharge specific capacity is respectively 135.6mAh/g, 102.5mAh/g.
Embodiment two
The first step is mixed 0.5mol lithium carbonate, 1mol diammonium hydrogen phosphate, 0.99mol ferrous oxalate, 0.01mol lanthanum acetate and 8.0g epoxy resin, is dispersant with 162.0g ethanol, mixes through the high speed ball milling;
Second step placed pit-type furnace with mixed raw material, fed nitrogen and protected, and heated 10 hours down at 300 ℃, must contain PO after cooling off, grinding 4 3-, Li +, La 2+, Fe 2+Reaction precursor body with carbon black;
The 3rd step was put into reactor with the reaction precursor body, placed pit-type furnace, fed nitrogen and protected, and calcined 24 hours down at 650 ℃, with promptly getting LiFe after the stove cooling 0.99La 0.01PO 4/ C composite doping modification positive electrode.
Adopt above-mentioned composite doping modification positive electrode to make cathode film as positive active material, cathode film consist of m Active material: m Acetylene black: m Ptfe emulsion (solid content)=80: 15: 5, thickness≤0.1mm made positive plate with the cathode film roll extrusion on stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard2300); Electrolyte is 1mol/LLiPF 6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas, at room temperature carry out charge-discharge test, and the charging/discharging voltage scope is 2.8~4.3V.When this material discharged and recharged with the 0.2C multiplying power, its first discharge specific capacity reached 159.4mAh/g; Specific discharge capacity after 100 charge and discharge cycles is 156.2mAh/g, and capability retention is 98.0%; During with 1.0C, 5.0C rate charge-discharge, its first discharge specific capacity is respectively 152.6mAh/g, 124.8mAh/g.(as shown in Figure 1, 2, 3)
Embodiment three
The first step is mixed 0.5mol lithium carbonate, 1mol ammonium phosphate, 0.98mol ferrous acetate, 0.02mol acetic acid neodymium and 18g cellobiose, is dispersant with 140.0g ethanol, mixes through the high speed ball milling;
Second step placed pit-type furnace with mixed raw material, fed nitrogen and protected, and heated 5 hours down at 350 ℃, must contain PO after cooling off, grinding 4 3-, Li +, Nd 2+, Fe 2+Reaction precursor body with carbon black;
The 3rd step was put into reactor with the reaction precursor body, placed pit-type furnace, fed nitrogen and protected, and calcined 30 hours down at 700 ℃, with promptly getting LiFe after the stove cooling 0.98Nd 0.02PO 4/ C composite doping modification positive electrode.
Adopt above-mentioned composite doping modification positive electrode to make cathode film as positive active material, cathode film consist of m Active material: m Acetylene black: m Ptfe emulsion (solid content)=80: 15: 5, thickness≤0.1mm made positive plate with the cathode film roll extrusion on stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard2300); Electrolyte is 1mol/LLiPF 6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas, at room temperature carry out charge-discharge test, and the charging/discharging voltage scope is 2.8~4.3V.When this material discharged and recharged with the 0.2C multiplying power, its first discharge specific capacity reached 150.4mAh/g; Specific discharge capacity after 100 charge and discharge cycles is 146.2mAh/g, and capability retention is 98.0%; During with 1.0C, 5.0C rate charge-discharge, its first discharge specific capacity is respectively 142.3mAh/g, 115.4mAh/g.
Embodiment four
The first step is mixed 1mol lithium acetate, 1mol ammonium dihydrogen phosphate, 0.97mol ferrous oxalate, 0.03mol cerous acetate and 3.6g cyclodextrin, is dispersant with 210.5g ethanol, mixes through the high speed ball milling;
Second step placed pit-type furnace with mixed raw material, fed nitrogen and protected, and heated 15 hours down at 400 ℃, must contain PO after cooling off, grinding 4 3-, Li +, Ce 2+, Fe 2+Reaction precursor body with carbon black;
The 3rd step was put into reactor with the reaction precursor body, placed pit-type furnace, fed nitrogen and protected, and calcined 40 hours down at 800 ℃, with promptly getting LiFe after the stove cooling 0.97Ce 0.03PO 4/ C composite doping modification positive electrode.
Adopt above-mentioned composite doping modification positive electrode to make cathode film as positive active material, cathode film consist of m Active material: m Acetylene black: m Ptfe emulsion (solid content)=80: 15: 5, thickness≤0.1mm made positive plate with the cathode film roll extrusion on stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard2300); Electrolyte is 1mol/LLiPF 6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas, at room temperature carry out charge-discharge test, and the charging/discharging voltage scope is 2.8~4.3V.When this material discharged and recharged with the 0.2C multiplying power, its first discharge specific capacity reached 139.8mAh/g; Specific discharge capacity after 100 charge and discharge cycles is 132.5mAh/g, and capability retention is 98.0%; During with 1.0C, 5.0C rate charge-discharge, its first discharge specific capacity is respectively 132.5mAh/g, 99.6mAh/g.
As mentioned above, can realize the present invention preferably.

Claims (10)

1, a kind of preparation method of composite doping modification lithium-ion battery anode material is characterized in that, comprises the steps and process conditions:
The first step is with the compound of compound and the amorphous phase doped chemical C of Li source compound, P source compound, Fe source compound, crystalline phase doped with rare-earth elements M, wherein the mol ratio of Li: Fe: P: M is 1: (0.97~0.995): 1: (0.005~0.03), and the addition of the compound of amorphous phase doped chemical C is 1~10wt% of mixture gross mass;
Second step heated mixed raw material 5~20 hours down at 250~400 ℃, obtained containing PO after cooling, the grinding 4 3-, Li +, M N+, Fe 2+Reaction precursor body with carbon black;
The 3rd step calcined the reaction precursor body 10~40 hours down at 500~800 ℃, promptly got LiFe after the cooling (1-x)M xPO 4/ C composite doping modification lithium-ion battery anode material.
According to the preparation method of the described a kind of composite doping modification lithium-ion battery anode material of claim 1, it is characterized in that 2, described Li source compound is one or more mixtures in lithium nitrate, lithium carbonate, the lithium acetate.
According to the preparation method of the described a kind of composite doping modification lithium-ion battery anode material of claim 1, it is characterized in that 3, described P source compound is one or more mixtures in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, the diammonium hydrogen phosphate.
According to the preparation method of the described a kind of composite doping modification lithium-ion battery anode material of claim 1, it is characterized in that 4, described Fe source compound is a kind of or their mixture in ferrous oxalate, the ferrous acetate.
According to the preparation method of the described a kind of composite doping modification lithium-ion battery anode material of claim 1, it is characterized in that 5, the compound of described crystalline phase doped with rare-earth elements M is one or more mixtures in lanthanum acetate, acetic acid yttrium, acetic acid neodymium, the cerous acetate.
6, according to the preparation method of the described a kind of composite doping modification lithium-ion battery anode material of claim 1, it is characterized in that the compound of described amorphous phase doped chemical C is one or more mixtures in glucose, epoxy resin, cellobiose, the cyclodextrin.
7, according to the preparation method of the described a kind of composite doping modification lithium-ion battery anode material of claim 1, it is characterized in that, the described first step is to be dispersant with ethanol, and the addition of ethanol is 40~60wt% of mixture gross mass, through the high speed ball milling raw material is mixed and is uniformly dispersed.
According to the preparation method of the described a kind of composite doping modification lithium-ion battery anode material of claim 1, it is characterized in that 8, described second step is that mixed raw material is put into pit-type furnace, feed the protection of nitrogen do and add thermal response.
According to the preparation method of the described a kind of composite doping modification lithium-ion battery anode material of claim 1, it is characterized in that 9, described the 3rd step is that the reaction precursor body is put into reactor, places pit-type furnace, feed nitrogen do protection carrying out calcination reaction.
10, a kind of composite doping modification lithium-ion battery anode material is prepared from by the described method of claim 1 exactly.
CNB2006101237861A 2006-11-27 2006-11-27 Composite doped modified lithium-ion battery anode material and its manufacture method Expired - Fee Related CN100490221C (en)

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CN101789504B (en) * 2010-03-17 2012-03-14 中南大学 Preparation method of nano LiFel-xMxPO4/C lithium phosphate composite positive pole material
CN101931075B (en) * 2010-06-28 2013-07-03 彩虹集团公司 Rare earth-doped power battery anode material and preparation method thereof
CN102044660A (en) * 2010-10-30 2011-05-04 华南理工大学 Rare-earth element samarium-doped modified lithium ion battery anode material and preparation method thereof
CN102544500A (en) * 2012-03-22 2012-07-04 上海锦众信息科技有限公司 Lithium ion battery cathode material and preparation method thereof
CN106477546B (en) * 2016-10-14 2018-08-31 山东省科学院能源研究所 A kind of NH4Fe1-xMxPO4And LiFe1-xMxPO4The preparation method of/C-material
CN109080311A (en) * 2018-08-27 2018-12-25 宁波正霖文具有限公司 The novel erasable crayon of one kind and its manufacturing method

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