CN102544500A - Lithium ion battery cathode material and preparation method thereof - Google Patents
Lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- CN102544500A CN102544500A CN2012100780540A CN201210078054A CN102544500A CN 102544500 A CN102544500 A CN 102544500A CN 2012100780540 A CN2012100780540 A CN 2012100780540A CN 201210078054 A CN201210078054 A CN 201210078054A CN 102544500 A CN102544500 A CN 102544500A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium ion battery cathode material and a preparation method thereof. The method comprises the following steps: mixing lithium source compounds, phosphor source compounds, iron source compounds, compounds of rare earth element M, and compounds of noncrystalline phase doped element C, heating at 250-400 DEG C for 5-20 hours, cooling, grinding to obtain a reaction precursor containing PO4<3->, Li+, Mn+, Fe2+, and carbon black; calcining the reaction precursor at 750-900 DEG C for 15-35 hours, cooling to obtain the lithium ion battery cathode material, wherein in the compounds of rare earth element M, the molar ratio of light rare earth element compounds and heavy rare earth element compounds is 1:2-2:3. The preparation method of the invention can effectively control the chemical components, structures and particle sizes of composite doped modified cathode materials, improve the electronic conductivity and lithium ion diffusion rate of the materials, and improve the electrochemical performance of the materials; also can simplify the material synthetic process, and is convenient for large-scale production.
Description
Technical field
The present invention relates to technical field of chemical power, specifically be meant a kind of anode material for lithium-ion batteries 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 receives Li
+At LiFePO
4-FePO
4Diffusion velocity between two phases 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 through 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 (like conductive carbon black) or adopted crystalline phase to mix through amorphous phase.Like people [Electrochemistry Communications such as Yang Shou feng; 505～508 (3); People [Electrochemical and Solid State Letters such as the liquid-phase coprecipitation that people [Electrochemistry Communnications, 839～842 (5), 2003] such as the hydrothermal synthesis method that 2001] adopts, Park adopt, Croce F; A47～A50 (5); 2002] sol-gel processes that adopt etc. have been synthesized granularity respectively than homogeneous, tiny LiFePO 4 material, have improved the chemical property of material.G.Li and A.Yamada [WO 00/60679 (2000)] has 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 [Journal of The Electrochemical Society, 148 (8), 2001] such as Atsuo Yamada then synthesize Li (Mn through 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 process can synthesize granularity than homogeneous, LiFePO that particle diameter is more tiny
4The material powder has shortened the evolving path of Li+, but not obvious to the improvement of material electric conductivity, and said method also exists equipment requirements height or technology than shortcomings such as complicacies, is difficult for carrying out industrialization production.
2, adopt the method for simple doping carbon, the carbon black consumption is more, because the density of carbon black compares LiFePO
4Want much little, 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 technical process of doping metals powder method is prone to take place the metal dust sedimentation, 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 (M that element such as manganese or cobalt etc. generated
nYFe
1-y) PO
4, the material crystals stability of structure is reduced, thereby also influence the electrical property of material.
Summary of the invention
The object of the invention is exactly the weak point that exists in the above-mentioned prior art in order to solve, and a kind of anode material for lithium-ion batteries and preparation method thereof is provided.The present invention is that crystalline phase is a dopant with weight rare earth element M; Adopt the method for amorphous phase-crystalline phase codope; Come the synthesis modification positive electrode through 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.
According to rare earth element atom electron structure and physicochemical properties; And their symbiosis situation in mineral can produce characteristic of different nature with different ionic radius; 17 kinds of rare earth elements are divided into two groups usually, and light rare earth (claiming the cerium group again) comprising: lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium; Heavy rare earth (claiming the yttrium group again) comprising: terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, yttrium.
The object of the invention is realized through following technical scheme: the preparation method of said a kind of anode material for lithium-ion batteries comprises the steps and process conditions:
The first step; Compound with compound and the amorphous phase doped chemical C of Li source compound, P source compound, Fe source compound, rare earth element M; Wherein the mol ratio of Li: Fe: P: M is 1: (0.97～0.995): 1: (0.04～0.045), and the addition of the compound of amorphous phase doped chemical C is 2～10wt% of mixture gross mass;
Second step, mixed raw material was heated 5～20 hours down at 250～400 ℃, obtain containing PO after cooling, the grinding
4 3-, Li
+, Mn
+, Fe
2+Reaction precursor body with carbon black;
The 3rd step, the reaction precursor body was calcined 15-35 hour down at 750～900 ℃, promptly get LiFe after the cooling
(1-x)M
xPO
4/ C anode material for lithium-ion batteries; Wherein in the compound of rare earth element M, the mol ratio of the compound of LREE and the compound of heavy rare earth element is 1:2 ~ 2:3.
In order to realize the present invention better, said Li source compound is one or more mixtures in lithium nitrate, lithium carbonate, the lithium acetate; Said P source compound is one or more mixtures in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, the diammonium hydrogen phosphate; Said Fe source compound is a kind of or their mixture in ferrous oxalate, the ferrous acetate; The compound of said crystalline phase doped with rare-earth elements M is one or more mixtures in lanthanum acetate, cerous acetate, acetic acid yttrium, the acetic acid lutetium; The compound of said amorphous phase doped chemical C is one or more mixtures in glucose, epoxy resin, the cyclodextrin; The said 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 materials mix is uniformly dispersed; Said second step is mixed raw material to be put into Muffle furnace carry out reacting by heating; Said 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 anode material for lithium-ion batteries according to the invention forms through 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 (Mn
+) get into 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 the embedding of Li+ 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; In addition, feel free to try and adopt the weight rare earth element to make up according to a certain percentage, effectively adjusted the positive electrode internal crystal structure, its electrical property increases significantly.
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 162.3mAh/g to this material, is 95.4% of theoretical specific capacity with 0.2C rate charge-discharge voltage range; Specific discharge capacity after 100 charge and discharge cycles is 158.1mAh/g, and capability retention is 99.0%.
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 155.2mAh/g, 130.1mAh/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 LiFe0.99La0.015Y0.03PO of embodiment one
4The X-ray diffracting spectrum of/C;
Fig. 2 is the prepared LiFe0.99La0.015Y0.03PO of embodiment one
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/LLiPF6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1), and charge-discharge magnification is 0.2C;
Fig. 3 is the discharge curve that embodiment one prepared LiFe0.99La0.015Y0.03PO4/C is assembled into the circulation of rate charge-discharge first behind the Experimental cell; The charging/discharging voltage scope is 2.8～4.3V; Electrolyte is 1mol/LLiPF6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1), and charge-discharge magnification is respectively 1.0C, 5.0C.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is done further detailed description, but execution mode of the present invention is not limited thereto.
Embodiment one
The first step is mixed lanthanum acetate and the 36.0g glucose of 1mol lithium nitrate, 1mol phosphoric acid, 0.995mol ferrous acetate, 0.03mol acetic acid yttrium, 0.015mol, 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+, 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 20 hours down at 750 ℃, with promptly getting the modification positive electrode after the stove cooling.
Adopt above-mentioned composite doping modification positive electrode to process cathode film as positive active material; Cathode film consist of the m active material: m acetylene black: m ptfe emulsion (solid content)=80: 15: 5; Thickness≤0.1mm processes 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/L LiPF
6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1); In the glove box of applying argon gas, be assembled into Experimental cell, at room temperature carry out charge-discharge test, the charging/discharging voltage scope is 2.8～4.3V; Its first discharge specific capacity reaches 162.3mAh/g, is 95.4% of theoretical specific capacity; Specific discharge capacity after 100 charge and discharge cycles is 158.1mAh/g, and capability retention is 99.0%; During with 1.0C, 5.0C rate charge-discharge, its first discharge specific capacity is respectively 155.2mAh/g, 130.1mAh/g.
Embodiment two
The first step is mixed 0.5mol lithium carbonate, 1mol diammonium hydrogen phosphate, 0.99mol ferrous oxalate, 0.015mol cerous acetate, 0.03mol lutecium nitrate 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
+, Ce
2+, Lu
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 800 ℃, with promptly getting the modification positive electrode after the stove cooling.
Adopt above-mentioned composite doping modification positive electrode to process cathode film as positive active material; Cathode film consist of the m active material: m acetylene black: m ptfe emulsion (solid content)=80: 15: 5; Thickness≤0.1mm processes 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/L LiPF
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 160.0mAh/g; Specific discharge capacity after 100 charge and discharge cycles is 156.3mAh/g, and capability retention is 98.0%; During with 1.0C, 5.0C rate charge-discharge, its first discharge specific capacity is respectively 152.5mAh/g, 124.6mAh/g (like Fig. 1,2, shown in 3).
It will be recognized by those skilled in the art, under the prerequisite that does not depart from protection scope of the present invention, can carry out various modifications, variation and combination, and think that this modification, variation and combination are within the scope of originality thought above-mentioned execution mode.
Claims (10)
1. the preparation method of an anode material for lithium-ion batteries is characterized in that, comprises the steps and process conditions:
(1) with the compound of compound and the amorphous phase doped chemical C of Li source compound, P source compound, Fe source compound, rare earth element M; Wherein the mol ratio of Li: Fe: P: M is 1: (0.97～0.995): 1: (0.04～0.045), and the addition of the compound of amorphous phase doped chemical C is 2～10wt% of mixture gross mass;
(2) mixed raw material was heated 5～20 hours down at 250～400 ℃, obtain containing the reaction precursor body of PO43-, Li+, Mn+, Fe2+ and carbon black after cooling, the grinding;
(3) the reaction precursor body was calcined 15-35 hour down at 750～900 ℃, promptly got LiFe (1-x) MxPO4/C anode material for lithium-ion batteries after the cooling;
Wherein in the compound of rare earth element M, the mol ratio of the compound of LREE and the compound of heavy rare earth element is 1:2 ~ 2:3.
2. preparation method according to claim 1 is characterized in that, said Li source compound is one or more mixtures in lithium nitrate, lithium carbonate, the lithium acetate.
3. preparation method according to claim 1 is characterized in that, said P source compound is one or more mixtures in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, the diammonium hydrogen phosphate.
4. preparation method according to claim 1 is characterized in that, said Fe source compound is a kind of or their mixture in ferrous oxalate, the ferrous acetate.
5. preparation method according to claim 1 is characterized in that, the compound of said crystalline phase doped with rare-earth elements M is one or more mixtures in lanthanum acetate, cerous acetate, acetic acid yttrium, the acetic acid lutetium.
6. preparation method according to claim 1 is characterized in that, the compound of said amorphous phase doped chemical C is one or more mixtures in glucose, epoxy resin, the cyclodextrin.
7. preparation method according to claim 1 is characterized in that, the said 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 materials mix is uniformly dispersed.
8. preparation method according to claim 1 is characterized in that, said second step is mixed raw material to be put into Muffle furnace carry out reacting by heating.
9. preparation method according to claim 1 is characterized in that, said the 3rd step is that the reaction precursor body is put into reactor, places pit-type furnace, feeds nitrogen do protection carrying out calcination reaction.
10. anode material for lithium-ion batteries is through being prepared from like the said method of one of claim 1-9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887504A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for preparing carbon material for lithium ion battery cathode |
| CN114956209A (en) * | 2022-06-27 | 2022-08-30 | 蜂巢能源科技股份有限公司 | Medium-low nickel cobalt-free cathode material with single crystal structure and preparation method and application thereof |
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| CN1964105A (en) * | 2006-11-27 | 2007-05-16 | 华南理工大学 | Composite doping modification lithium-ion battery anode material and its manufacture method |
| CN101546831A (en) * | 2008-03-28 | 2009-09-30 | 潘树明 | Lithium ion battery anode material composite lithium iron phosphate and four-step synthesis and preparation process thereof |
| CN102104148A (en) * | 2010-12-31 | 2011-06-22 | 北京中科浩运科技有限公司 | Mixed rare earth compound-doped and modified lithium iron phosphate cathode material and preparation method thereof |
| US20110300442A1 (en) * | 2010-06-02 | 2011-12-08 | Infinity Energy (Hong Kong) Co., Limited | Novel nanoscale solution method for synthesizing lithium cathode active materials |
-
2012
- 2012-03-22 CN CN2012100780540A patent/CN102544500A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1964105A (en) * | 2006-11-27 | 2007-05-16 | 华南理工大学 | Composite doping modification lithium-ion battery anode material and its manufacture method |
| CN101546831A (en) * | 2008-03-28 | 2009-09-30 | 潘树明 | Lithium ion battery anode material composite lithium iron phosphate and four-step synthesis and preparation process thereof |
| US20110300442A1 (en) * | 2010-06-02 | 2011-12-08 | Infinity Energy (Hong Kong) Co., Limited | Novel nanoscale solution method for synthesizing lithium cathode active materials |
| CN102104148A (en) * | 2010-12-31 | 2011-06-22 | 北京中科浩运科技有限公司 | Mixed rare earth compound-doped and modified lithium iron phosphate cathode material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887504A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for preparing carbon material for lithium ion battery cathode |
| CN102887504B (en) * | 2012-09-24 | 2016-08-17 | 上海锦众信息科技有限公司 | A kind of preparation method of carbon material for lithium ion battery cathode |
| CN114956209A (en) * | 2022-06-27 | 2022-08-30 | 蜂巢能源科技股份有限公司 | Medium-low nickel cobalt-free cathode material with single crystal structure and preparation method and application thereof |
| CN114956209B (en) * | 2022-06-27 | 2024-02-27 | 蜂巢能源科技股份有限公司 | Medium-low nickel cobalt-free positive electrode material with single crystal structure, and preparation method and application thereof |
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Application publication date: 20120704 |