CN103956458A - Composite positive electrode of lithium ion battery as well as preparation method and application to all-solid-state battery thereof - Google Patents
Composite positive electrode of lithium ion battery as well as preparation method and application to all-solid-state battery thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention discloses a composite positive electrode of a lithium ion battery as well as a preparation method and application to an all-solid-state battery thereof. The composite positive electrode of the lithium ion battery comprises a positive active material, inorganic solid electrolyte and a conductive oxide additive, wherein the positive active material is any one of lithium cobaltate, lithium manganate, lithium iron phosphate and nickel-cobalt-manganese ternary material; the inorganic solid electrolyte is at least one of lithium borate, lithium metaborate and lithium fluoride; the conductive oxide additive is any one of indium tin oxide, indium oxide, tin dioxide, zinc oxide, nickel oxide and ferroferric oxide. The method comprises the steps of (1) mixing the positive active material, the inorganic solid electrolyte and the conductive oxide additive, carrying out ball milling, drying, and carrying out tabletting to obtain a ceramic piece; and (2) sintering the ceramic piece to obtain the composite positive electrode. The composite positive electrode is good in mass ratio capacity, area ratio capacity and cycle performance, can be used for preparing the all-solid-state lithium ion battery, and can be used at high temperature.
Description
Technical field
The present invention relates to a kind of composite lithium ion battery anode and preparation method thereof and application in assembling all solid state lithium ion battery, belong to technical field of lithium ion.
Background technology
Lithium ion battery have energy density high, have extended cycle life, the advantage such as memory-less effect, in as business-like high-efficiency energy-storage device, being widely used in daily life, producing.Yet the potential safety hazard that in commercial li-ion battery, flammable organic electrolyte produces remains the significant challenge of puzzlement lithium ion battery, especially in the large-scale application fields such as electric automobile and energy-accumulating power station.
All solid state lithium ion battery is used solid electrolyte to substitute the organic liquid electrolyte using in commercial li-ion battery, can fundamentally solve the safety problem of lithium ion battery.At present, mostly concentrate on solid electrolyte, and obtained significant achievement about the research of all solid state lithium ion battery, the lithium ion conductivity of a lot of system solid electrolytes has all reached 10
-4s/cm, has met the requirement of all solid state lithium ion battery to electrolytic conductivity substantially.And the structural design of the structural design of all-solid-state battery, especially anode composite remains all solid state lithium ion battery urgent problem.
Composite lithium ion battery anode is comprised of positive active material, inorganic solid electrolyte and conductive additive, by introducing inorganic solid electrolyte, provides transmission channel for lithium ion; By introducing conductive additive, provide electron propagation ducts; By increasing the contact area of electrolyte and positive active material, effectively solve interface problem, shorten the migration distance of lithium ion in the positive active material of low lithium ion conductivity, guaranteed positive active material sufficient redox reaction in battery charge and discharge process.Insider generally believes that all solid state lithium ion battery that is applicable to extensive use should be used anode composite.
At present about the research of composite lithium ion battery anode, mostly using sulphur is electrolyte.Sulphur is that electrolyte softening temperature is low, composite construction is easily prepared, but to airborne moisture-sensitive, brings a lot of problems to preparation, test and application.In addition, sulphur is that the interface of electrolyte and part positive electrode material is unstable, also needs to utilize oxide to be coated processing, complex process to positive electrode before use.The oxide electrolysis plastidome anode composite of having reported is all generally film-type or thick-film type, and the thickness of anode composite is all no more than 10 μ m, and this has seriously limited the Area Ratio capacity of anode composite and the energy density of all-solid-state battery.In addition, the oxide electrolysis plastidome anode composite of having reported does not all add conductive additive, has seriously limited the chemical property of anode composite when high magnification, high current charge-discharge.
Summary of the invention
The object of this invention is to provide a kind of composite lithium ion battery anode and preparation method thereof and application in assembling all solid state lithium ion battery, the all solid state lithium ion battery being obtained by anode composite assembling of the present invention has good Area Ratio capacity and energy density, and can at high temperature use.
Composite lithium ion battery anode provided by the invention, it is comprised of positive active material, inorganic solid electrolyte and oxidation conductive additive;
Described positive active material is any in cobalt acid lithium, LiMn2O4, LiFePO4 and nickel-cobalt-manganese ternary material;
Described inorganic solid electrolyte is at least one in lithium borate, lithium metaborate and lithium fluoride;
Described oxide conducting additive is any in tin indium oxide, indium oxide, tin ash, zinc oxide, nickel oxide and tri-iron tetroxide.
In above-mentioned composite lithium ion battery anode, the mass fraction of described positive active material can be 40%~90%, specifically can be: 40%~70%, 70%~90%, 40%, 70%, 80% or 90%;
The mass fraction of described inorganic solid electrolyte can be 5%~40%, specifically can be 5%~20%, 10%~20%, 10%~40%, 20%~40%, 5%, 10%, 20% or 40%;
The mass fraction of described oxide conducting additive can be 5%~30%, specifically can be: 5%~20%, 10%~20%, 5%, 10% or 20%.
In above-mentioned composite lithium ion battery anode, the chemical formula of described nickel-cobalt-manganese ternary material is LiNi
xco
ymn
zo
2, the value of x, y and z is as follows: x is that 0.5, y is that 0.2, z is 0.3; X is that 0.4, y is that 0.2, z is 0.4; Or x is that 0.33, y is that 0.33, z is 0.33; X, y and z represent respectively the stoichiometric number of element Ni, Co and Mn.
In above-mentioned composite lithium ion battery anode, described inorganic solid electrolyte can be following 1) or 2):
1) mixture of described lithium metaborate and described lithium fluoride, the mass ratio of described lithium metaborate and described lithium fluoride is 1~3:1; Specifically can be 3:1;
2) mixture of described lithium borate, described lithium metaborate and described lithium fluoride, the mass ratio of described lithium borate, described lithium metaborate and described lithium fluoride can be 1:1:1.
Composite lithium ion battery anode of the present invention is not strict with the particle diameter of adopted positive active material, inorganic solid electrolyte and oxide conducting additive granules, and commercially available above-mentioned substance particle or powder all can meet requirement of the present invention conventionally.
Composite lithium ion battery anode provided by the invention has good specific discharge capacity, Area Ratio capacity and cycle performance, and by adding the method for conductive oxide, has strengthened electronic conductivity and the high rate performance of anode composite.
The present invention also provides the preparation method of described composite lithium ion battery anode, comprises the steps:
(1) described positive active material, described inorganic solid electrolyte and described oxide conducting additive are carried out to ball milling, after drying, be pressed into potsherd;
Described positive active material can be any in cobalt acid lithium, LiMn2O4, LiFePO4 and nickel-cobalt-manganese ternary material;
Described inorganic solid electrolyte can be at least one in lithium borate, lithium metaborate and lithium fluoride;
Described oxide conducting additive can be any in tin indium oxide, indium oxide, tin ash, zinc oxide, nickel oxide and tri-iron tetroxide;
(2) by described potsherd sintering and get final product.
In above-mentioned preparation method, in step (1), the time of described ball milling can be 4~36 hours, specifically can be 4 hours~24 hours, 12 hours~36 hours, 12 hours~24 hours, 4 hours, 12 hours, 24 hours or 36 hours;
The temperature of described oven dry can be 50~150 ℃, specifically can be 50~100 ℃, 70~150 ℃, 50 ℃, 70 ℃, 100 ℃ or 150 ℃; The time of described oven dry can be 2~12 hours, specifically can be 2 hours~6 hours, 6 hours~10 hours, 10 hours~12 hours, 2 hours, 6 hours, 10 hours or 12 hours.
In above-mentioned preparation method, in step (1), the mass ratio of described positive active material, described inorganic solid electrolyte and described oxide conducting additive can be 40~90:5~30:5~30, specifically can be 80:10:10,90:5:5,40:40:20 or 70:20:10.
In above-mentioned preparation method, in step (2), the temperature of described sintering can be 700 ℃~1100 ℃, specifically can be 700 ℃~1000 ℃, 800 ℃~1100 ℃, 800~1000 ℃, 700 ℃, 800 ℃, 1000 ℃ or 1100 ℃;
The time of described sintering can be 0.5~10 hour, specifically can be 0.5 hour~4 hours, 2 hours~10 hours, 4 hours~10 hours, 0.5 hour, 2 hours, 4 hours or 10 hours;
In the process of described sintering, the described inorganic solid electrolyte of low melting point can melt, and then be penetrated between described positive active material and described oxide conducting additive granules, in cooling procedure, solidify and described positive active material and described oxide conducting additive are bonded together, forming the anode composite of high-compactness.
The preparation method of composite lithium ion battery anode provided by the invention, adopts ball milling mixed cathode active material, inorganic solid electrolyte and oxide conducting additive, and prepares by sintering.The introducing of low melting point inorganic solid electrolyte can reduce sintering temperature, and the introducing of oxide conducting additive can increase the electronic conductivity of anode composite.Meanwhile, all anode composite components are all stable under high temperature, air atmosphere, so prepared by anode composite low-temperature sintering under air atmosphere.
The present invention also provides the application of described composite lithium ion battery anode in assembling all solid state lithium ion battery.
All solid state lithium ion battery provided by the present invention, is comprised of described composite lithium ion battery anode, full solid state polymer electrolyte layer and lithium anode;
Before the described all solid state lithium ion battery of assembling, can also grind to described composite lithium ion battery anode the step of slabbing.
In above-mentioned all solid state lithium ion battery, the thickness of described composite lithium ion battery anode can be 100~1000 microns, specifically can be 100~500 microns, 150~1000 microns, 500~1000 microns, 100 microns, 150 microns, 500 microns or 1000 microns;
The thickness of described full solid state polymer electrolyte layer can be 10~200 microns, specifically can be 40 microns.
While assembling described all solid state lithium ion battery, the full solid state polymer electrolyte kind adopting is restriction not, and report and commercially available full solid state polymer electrolyte all can meet requirement of the present invention conventionally.
All solid state lithium ion battery provided by the invention has good Area Ratio capacity and energy density, and can at high temperature use.
Described all solid state lithium ion battery can be prepared by following method:
(1) in glove box, configuration full solid state polymer electrolyte solution, and solution is dripped and is attached on the anode composite preparing, natural drying 6~24 hours;
(2) lithium sheet is attached on all solid state electrolyte, utilizes button cell encapsulation, obtain all-solid-state battery.
Tool of the present invention has the following advantages:
(1) composite lithium ion battery anode provided by the invention can be applicable to the preparation of all solid state lithium ion battery widely, can improve the interface problem between solid electrolyte and positive active material, shorten the migration distance of lithium ion in positive active material, thereby improve energy density and the cycle performance of all-solid-state battery;
(2) all solid state lithium ion battery provided by the invention, its preparation technology is simple, and has good Area Ratio capacity and energy density, and can at high temperature use.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the composite lithium ion battery anode section of the embodiment of the present invention 2 preparations.
Fig. 2 is the composite lithium ion battery anode of the embodiment of the present invention 1 preparation discharge capacity curve in 20 charge and discharge cycles.
Structural representation and the charging and discharging curve of the all-solid-state battery of Fig. 3 embodiment of the present invention 5 preparations.
Embodiment
The experimental technique using in following embodiment if no special instructions, is conventional method.
In following embodiment, material used, reagent etc., if no special instructions, all can obtain from commercial channels.
Embodiment 1, prepare composite lithium ion battery anode
(1) by nickel-cobalt-manganese ternary material (LiNi
0.5co
0.2mn
0.3o
2) positive active material, lithium metaborate and lithium fluoride hybrid solid-state electrolyte (mass ratio 3:1), after tin indium oxide conductive additive mixes, then carry out ball milling and mix 12 hours, in 70 ℃ of oven dry 10 hours, the mixed powder after drying is pressed into potsherd;
(2) by potsherd 1000 ℃ of sintering 2 hours, obtain anode composite, and with sand paper, thickness ground to 150 microns.
In composite lithium ion battery anode prepared by the present embodiment, the mass fraction of nickel-cobalt-manganese ternary material is 80%, and lithium metaborate and the electrolytical mass fraction of lithium fluoride hybrid solid-state are 10%, and the mass fraction of tin indium oxide conductive additive is 10%.
Embodiment 2, prepare composite lithium ion battery anode
(1) after lithium cobaltate cathode active material, lithium borate solid electrolyte and tin ash conductive additive are mixed, then carry out ball milling and mix 24 hours, in 100 ℃ of oven dry 6 hours, the mixed powder after drying is pressed into potsherd;
(2) by potsherd 700 ℃ of sintering 10 hours, obtain anode composite, and thickness ground into the sheet of 1000 microns with sand paper.
In composite lithium ion battery anode prepared by the present embodiment, the mass fraction of cobalt acid lithium is 90%, and the mass fraction of lithium borate solid electrolyte is 5%, and the mass fraction of tin ash conductive additive is 5%.
Embodiment 3, prepare composite lithium ion battery anode
(1) by lithium manganate cathode active material, lithium borate, lithium metaborate and lithium fluoride hybrid solid-state electrolyte (mass ratio 1:1:1), after nickel oxide conductive additive mixes, then carry out ball milling and mix 36 hours, in 150 ℃ of oven dry 2 hours, the mixed powder after drying is pressed into potsherd;
(2) by potsherd 800 ℃ of sintering 4 hours, obtain anode composite, and with sand paper, thickness ground to 500 microns.
In composite lithium ion battery anode prepared by the present embodiment, the mass fraction of LiMn2O4 is 40%, and lithium borate, lithium metaborate and the electrolytical mass fraction of lithium fluoride hybrid solid-state are 40%, and the mass fraction of nickel oxide conductive additive is 20%.
Embodiment 4, prepare composite lithium ion battery anode
(1), by iron phosphate lithium positive pole active material, lithium fluoride solid electrolyte, after zinc oxide conductive additive mixes, then carries out ball milling and mixes 4 hours, in 50 ℃ of oven dry 12 hours, the mixed powder after drying is pressed into potsherd;
(2) by potsherd 1100 ℃ of sintering 0.5 hour, obtain anode composite, and with sand paper, thickness ground to 100 microns.
In composite lithium ion battery anode prepared by the present embodiment, the mass fraction of LiFePO4 is 70%, and the mass fraction of lithium fluoride solid electrolyte is 20%, and the mass fraction of zinc oxide conductive additive is 10%.
Embodiment 5, prepare all solid state lithium ion battery
(1) in glove box, (polymer dielectric matrix is chlorohydrin rubber to preparation full solid state polymer electrolyte solution, lithium salts is two fluoroform sulfimide lithiums, solvent is acetone), and solution is dripped and is attached to the nickel-cobalt-manganese ternary Material cladding preparing anodal (anode composite of embodiment 1 preparation) above, natural drying 18 hour;
(2) lithium sheet is attached on all solid state electrolyte after drying, utilizes button cell encapsulation, obtain all-solid-state battery.
In all solid state lithium ion battery prepared by the present embodiment, the thickness of anode composite is 150 microns, and the thickness of full solid state polymer electrolyte layer is 40 microns.
The performance test of embodiment 6, composite lithium ion battery anode and all solid state lithium ion battery
One, the scanning electron microscope (SEM) photograph of section
Anode composite section brittle failure prepared by the present invention, section spray carbon, is placed in ESEM, regulates and focuses on and except astigmatism, obtain sample section pattern picture under suitable multiplication factor.
Fig. 1 is the profile scanning Electronic Speculum picture of the composite lithium ion battery anode of embodiment 2 preparations, and as can be seen from Figure 2, sample section is fine and close, there is no cavity, illustrates that the compactness of anode composite is good.
Two, charge and discharge cycles capacity
By metal spraying electrode of anode composite of embodiment 1 preparation, utilize metal lithium sheet as negative pole, add barrier film and perfusion organic electrolyte (bath composition 1mol/L lithium hexafluoro phosphate is dissolved in the ethylene carbonate that volume ratio is 1:1 (EC) and diethyl carbonate (DEC) mixed solution), assembling button cell, and in 3~4.3V voltage range, the multiplying power of C/15 is carried out charge-discharge test.
Fig. 2 is the charge and discharge cycles capacity curve of the anode composite of embodiment 1 preparation, can find out, in the circulation of 20 tests, the discharge capacity of sample is stable, and specific discharge capacity has reached 140mAh/g.
Three, the structural representation of all-solid-state battery and charging and discharging curve
Fig. 3 is structural representation and the charging and discharging curve of all solid state lithium ion battery of embodiment 5 preparations.
In structural representation, CE represents anode composite, and SE represents full solid state polymer electrolyte layer, and Li represents lithium anode, and this all solid state lithium ion battery structure is simple, and preparation easily.
From charging and discharging curve, can find out, this all-solid-state battery just has higher Area Ratio capacity, and can at high temperature use; And along with probe temperature improves, the performance of all-solid-state battery also increases.
Claims (9)
1. a composite lithium ion battery anode, is comprised of positive active material, inorganic solid electrolyte and oxidation conductive additive;
Described positive active material is any in cobalt acid lithium, LiMn2O4, LiFePO4 and nickel-cobalt-manganese ternary material;
Described inorganic solid electrolyte is at least one in lithium borate, lithium metaborate and lithium fluoride;
Described oxide conducting additive is any in tin indium oxide, indium oxide, tin ash, zinc oxide, nickel oxide and tri-iron tetroxide.
2. composite lithium ion battery anode according to claim 1, it is characterized in that: in described composite lithium ion battery anode, the mass fraction of described positive active material is 40%~90%, the mass fraction of described inorganic solid electrolyte is 5%~30%, and the mass fraction of described oxide conducting additive is 5%~30%.
3. composite lithium ion battery anode according to claim 1 and 2, is characterized in that: the chemical formula of described nickel-cobalt-manganese ternary material is LiNi
xco
ymn
zo
2, the value of x, y and z is as follows: x is that 0.5, y is that 0.2, z is 0.3; X is that 0.4, y is that 0.2, z is 0.4; Or x is that 0.33, y is that 0.33, z is 0.33.
4. according to the composite lithium ion battery anode described in any one in claim 1-3, it is characterized in that: described inorganic solid electrolyte is following 1) or 2):
1) mixture of described lithium metaborate and described lithium fluoride, the mass ratio of described lithium metaborate and described lithium fluoride is 1~3:1;
2) mixture of described lithium borate, described lithium metaborate and described lithium fluoride, the mass ratio of described lithium borate, described lithium metaborate and described lithium fluoride is 1:1:1.
5. the preparation method of composite lithium ion battery anode described in claim 1-4 any one, comprises the steps:
(1) by carrying out ball milling after described positive active material, described inorganic solid electrolyte and the mixing of described oxide conducting additive, after drying, be pressed into potsherd;
Described positive active material is any in cobalt acid lithium, LiMn2O4, LiFePO4 and nickel-cobalt-manganese ternary material;
Described inorganic solid electrolyte is at least one in lithium borate, lithium metaborate and lithium fluoride;
Described oxide conducting additive is any in tin indium oxide, indium oxide, tin ash, zinc oxide, nickel oxide and tri-iron tetroxide;
(2) by described potsherd sintering, obtain described composite lithium ion battery anode.
6. preparation method according to claim 5, is characterized in that: in step (1), the time of described ball milling is 4~36 hours; The temperature of described oven dry is 50~150 ℃, and the time is 2~12 hours;
The mass ratio of described positive active material, described inorganic solid electrolyte and described oxide conducting additive is 40~90:5~30:5~30;
In step (2), the temperature of described sintering is 700 ℃~1100 ℃, and the time is 0.5~10 hour.
7. the application of composite lithium ion battery anode in assembling all solid state lithium ion battery described in any one in claim 1-4.
8. an all solid state lithium ion battery, in claim 1-4, described in any one, composite lithium ion battery anode, full solid state polymer electrolyte layer and lithium anode form.
9. all solid state lithium ion battery described according to Claim 8, is characterized in that: the thickness of described composite lithium ion battery anode is 100~1000 microns;
The thickness of described full solid state polymer electrolyte layer is 10~200 microns.
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