CN105845909A - Positive electrode active material for lithium ion battery, preparation method for positive electrode active material, and lithium ion battery - Google Patents
Positive electrode active material for lithium ion battery, preparation method for positive electrode active material, and lithium ion battery Download PDFInfo
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- CN105845909A CN105845909A CN201610268679.1A CN201610268679A CN105845909A CN 105845909 A CN105845909 A CN 105845909A CN 201610268679 A CN201610268679 A CN 201610268679A CN 105845909 A CN105845909 A CN 105845909A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a positive electrode active material for a lithium ion battery. The chemical expression of the positive electrode active material for the lithium ion battery is (A)<1-x>.(LiC<6>)<x>, wherein x is greater than 0 and less than 1; A is selected from at least one kind of LiM<1>PO<4>, LiM<2>O<2> and LiM<3><2>O<4>; and M1, M2 or M3 is selected from at least one kind of iron, cobalt, manganese, nickel, aluminium, or vanadium. The positive electrode active material for the lithium ion battery provided by the invention is relatively high in capacity. The invention also provides a preparation method for the positive electrode active material for the lithium ion battery, wherein the preparation method comprises the following steps of providing an A precursor and an LiC<6> precursor; pre-sintering the A precursor at a constant temperature of 200-500 DEG C for 1-5h in a protective gas or in the air, then naturally cooling to the room temperature to obtain the pre-sintered A precursor; uniformly mixing the pre-sintered A precursor and the LiC<6> precursor at the molar ratio of 1-x to x to obtain the positive electrode active material precursor for the lithium ion battery; and then sintering the positive electrode active material precursor for the lithium ion battery at a constant temperature of 300-700 DEG C for 5min-2h to obtain the positive electrode active material for the lithium ion battery. The preparation method is unique and effective.
Description
Technical field
The present invention relates to field of lithium ion battery, be specifically related to a kind of anode active material of lithium ion battery and system thereof
Preparation Method and lithium ion battery.
Background technology
Along with mancarried electronic aid and electric automobile are more and more higher to the requirement of lithium ion battery energy density, energy
The research and development of the lithium ion battery material that density is high seem and become more and more important.
At present, conventional anode material for lithium-ion batteries includes cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4),
With LiFePO4 (LiFePO4) etc., the actual specific capacity of these three material is both less than greatly 160mAh/g, due to
Capacity is on the low side, these electrode materials the lithium ion battery energy density made is relatively low, it is difficult to meet battery to material
The high power capacity requirement of material.Therefore, it is necessary to provide the anode active material of lithium ion battery that a kind of capacity is higher.
Summary of the invention
For solving the problems referred to above, the invention provides a kind of anode active material of lithium ion battery.This lithium-ion electric
Pond positive electrode active materials is by existing conventional positive electrode active materials and LiC6It is composited, LiC6Capacity relatively
Height, substantially increases the capacity of conventional positive electrode active materials.Present invention also offers lithium ion cell positive to live
Property material preparation method, this preparation method is unique, effectively.
First aspect present invention provides a kind of anode active material of lithium ion battery, described lithium ion cell positive
The chemical expression of active material is (A)1-x·(LiC6)x, wherein, 0 < x < 1, A is LiM1PO4、LiM2O2
And LiM3 2O4In at least one, M1、M2Or M3Selected from in ferrum, cobalt, manganese, nickel, aluminum and vanadium extremely
Few one.
Wherein, the span of described x is 0.05≤x≤0.4.
Wherein, the Surface coating of described A has the first carbon-coating or described LiC6Surface coating have the second carbon-coating or
The Surface coating of described A has the first the most described LiC of carbon-coating6Surface coating have the second carbon-coating.
Wherein, when the Surface coating of described A has the first carbon-coating, the surface of described first carbon-coating and LiC6Table
Face is also wrapped on the 3rd carbon-coating, comprises described LiC in described 3rd carbon-coating simultaneously6The first carbon-coating is had with Surface coating
A；
As described LiC6Surface coating when having the second carbon-coating, the surface of described A and the surface of described second carbon-coating
It is also wrapped on the 3rd carbon-coating, comprises A in described 3rd carbon-coating simultaneously and Surface coating has the LiC of the second carbon-coating6；
When the Surface coating of described A has the first the most described LiC of carbon-coating6Surface coating when having the second carbon-coating, institute
The surface on the surface and described second carbon-coating of stating the first carbon-coating is also wrapped on the 3rd carbon-coating, same in described 3rd carbon-coating
Time comprise Surface coating and have the A of the first carbon-coating and Surface coating to have the LiC of the second carbon-coating6。
The capacity of the anode active material of lithium ion battery that first aspect present invention provides is higher, it addition, lithium ion
The good stability of battery anode active material, electric conductivity is preferable.
Second aspect present invention provides the preparation method of a kind of anode active material of lithium ion battery, including following
Step:
A presoma is provided；Described A is LiM1PO4、LiM2O2And LiM3 2O4In at least one, M1、M2
Or M3It is selected from as at least one in ferrum, cobalt, manganese, nickel, aluminum and vanadium, in protective gas or air, general
Described A presoma, after 200-500 DEG C of constant temperature pre-burning 1-5h, is naturally cooling to room temperature, before obtaining the A after pre-burning
Drive body；
LiC is provided6Presoma；
By the A presoma after described pre-burning and described LiC6After presoma is 1-x:x mix homogeneously according to mol ratio,
Obtain anode active material of lithium ion battery presoma, 0 < x < 1, then in protective gas, by described lithium
Ion battery positive electrode active materials presoma Isothermal sinter 5min-2h at 300-700 DEG C, obtains lithium ion battery
Positive electrode active materials, the chemical formula of described anode active material of lithium ion battery is (A)1-x·(LiC6)x, 0 < x < 1.
Wherein, by the concrete operations that described anode active material of lithium ion battery presoma sinters it is: by described lithium
Ion battery positive electrode active materials presoma is warming up to 400-600 DEG C with the heating rate of 1-5 DEG C/min, and constant temperature burns
After knot 5-10min, it is down to room temperature with the rate of temperature fall of 1-5 DEG C/min.
Wherein, described LiC6The preparation method of presoma is: provide with C as negative electrode, with Li as anode, with six
Lithium fluophosphate, tetraethylammonium tetrafluoroborate, LiBF4, lithium perchlorate, hexafluoro close arsenic (V) acid lithium, trifluoro
Methanesulfonic acid lithium, form solid polymer, gelatin polymer or bis trifluoromethyl sulfimide lithium are the electricity of electrolyte
Chemical cell, in protective gas, applies the voltage of 0.5-2.5V, makes from described to described electrochemical cell
The Li ionized out in anode+It is deposited on negative electrode C, obtains described LiC6Presoma.
Wherein, by the 40-100 DEG C of drying under vacuum of post-depositional negative electrode, by described LiC6Presoma is from institute
State to strip down on negative electrode and carry out ball milling or sand milling, obtain nano level LiC6Presoma.
Wherein, LiC6The particle diameter of presoma is 10-80nm.
The preparation method of a kind of anode active material of lithium ion battery that embodiment of the present invention second aspect provides, system
Preparation Method is unique, effective, and the anode active material of lithium ion battery capacity prepared is higher, it addition, lithium-ion electric
The good stability of pond positive electrode active materials, electric conductivity is preferable.
Third aspect present invention provides a kind of lithium ion battery, and this lithium ion battery comprises first aspect present invention
The anode active material of lithium ion battery provided.
The lithium ion battery that third aspect present invention provides has excellent discharge capacity.
The advantage of the embodiment of the present invention will partly illustrate, and a part according to description is
It will be apparent that or can be known by the enforcement of the embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is A and LiC in anode active material of lithium ion battery in an embodiment of the present invention6Clad structure
Schematic diagram；
Fig. 2 is the XRD (X-ray diffraction) of the anode active material of lithium ion battery that the embodiment of the present invention 1 prepares
Figure；
Fig. 3 is the charging and discharging curve figure of the lithium ion battery that the embodiment of the present invention 1 prepares；
Fig. 4 is the cycle performance figure of the lithium ion battery that the embodiment of the present invention 1 prepares；
Fig. 5 is the embodiment of the present invention 1 prepared lithium ion battery cycle performance figure under different multiplying.
Detailed description of the invention
The following stated is the preferred embodiment of the present invention, it is noted that for the ordinary skill of the art
For personnel, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these change
Enter and retouching is also considered as protection scope of the present invention.
First aspect present invention provides a kind of anode active material of lithium ion battery, and this lithium ion cell positive is lived
The chemical expression of property material is (A)1-x·(LiC6)x, wherein, 0 < x < 1, A is LiM1PO4、LiM2O2With
LiM3 2O4In at least one, M1、M2Or M3Selected from in ferrum, cobalt, manganese, nickel, aluminum and vanadium at least
A kind of.
In embodiment of the present invention, A is existing conventional positive electrode active materials, does not the most do particular restriction.
In the present invention one preferred implementation, A is LiCoO2、LiMn2O4Or LiFePO4。
In embodiment of the present invention, 0.01≤x≤0.6.
In embodiment of the present invention, 0.05≤x≤0.4, when in 0.05≤x≤0.4, anode active material of lithium ion battery,
A and LiC6There is applicable ratio, positive electrode active materials can be made to have preferable stability and preferable electrochemistry
Performance.
In embodiment of the present invention, 0.1≤x≤0.2.
In embodiment of the present invention, when A is LiM1PO4Time, the particle diameter of anode active material of lithium ion battery is for receiving
Meter level or micron order, preferably 10-100nm, anode active material of lithium ion battery compacted density is
2.3-2.5g/cm3.Owing to the capacity of anode active material of lithium ion battery and the compacted density of the present invention are higher, more
Be conducive to improving the energy density of battery, thus expand the application of battery prepared by this material.
In embodiment of the present invention, when A is LiM2O2Or LiM3 2O4Time, anode active material of lithium ion battery
Particle diameter is micron order, and preferably 1 μm-1000 μm, anode active material of lithium ion battery compacted density is
3.9-4.2g/cm3.Owing to the capacity of anode active material of lithium ion battery and the compacted density of the present invention are higher, more
Be conducive to improving the energy density of battery, thus expand the application of battery prepared by this material.
In embodiment of the present invention, the Surface coating of A has the first carbon-coating or LiC6Surface coating have the second carbon-coating,
Or the Surface coating of A has the first carbon-coating LiC simultaneously6Surface coating have the second carbon-coating.Refer here to the surface of A
Carbon-coating can be coated with and also can not be coated with carbon-coating, LiC6Surface can be coated with carbon-coating and also can not be coated with carbon-coating, lithium-ion electric
The surface of pond positive electrode active materials can be coated with carbon-coating also can not be coated with carbon-coating.
In embodiment of the present invention, the surface of A can be coated with carbon-coating.At the coated with carbon bed of A, A can be improved
Electric conductivity, the most also can stop the reunion of A.
In the present invention one preferred implementation, LiC6Surface can be coated with carbon-coating.At LiC6Coated with carbon bed,
LiC can be improved6Electric conductivity.
In the present invention one preferred implementation, the surface of anode active material of lithium ion battery can be coated with carbon-coating.?
Anode active material of lithium ion battery coated with carbon bed, can improve leading of anode active material of lithium ion battery
Electrically, the reunion of anode active material of lithium ion battery offspring can the most also be stoped.
As it is shown in figure 1, Fig. 1 is A and LiC in anode active material of lithium ion battery in an embodiment of the present invention6
Clad structure schematic diagram, in the present invention one preferred implementation, (1) from Fig. 1 is it can be seen that work as A
Surface coating when having the first carbon-coating 1, the surface of the first carbon-coating 1 and LiC6Surface be also wrapped on the 3rd carbon-coating 3,
Comprise LiC in 3rd carbon-coating 3 simultaneously6With the A that Surface coating has the first carbon-coating；
(2) from Fig. 1 are it can be seen that work as LiC6Surface coating when having the second carbon-coating 2, the surface of A and
The surface of two carbon-coatings 2 is also wrapped on the 3rd carbon-coating 3, comprises A simultaneously and Surface coating has the second carbon in the 3rd carbon-coating 3
The LiC of layer6；
(3) from Fig. 1 are it can be seen that the Surface coating working as A has the first carbon-coating 1 LiC simultaneously6Surface coating
When having the second carbon-coating 2, the surface of the first carbon-coating 1 and the surface of the second carbon-coating 2 are also wrapped on the 3rd carbon-coating 3, and the 3rd
Comprise Surface coating in carbon-coating 3 has the A of the first carbon-coating and Surface coating to have the LiC of the second carbon-coating simultaneously6。
Certainly, the surface of A and LiC6Surface can not be coated with carbon-coating, or the surface of A and LiC6Surface
All it is coated with carbon-coating, in this carbon-coating, comprises A and LiC simultaneously6。
In the present invention one preferred implementation, when A is LiM1PO4Time, the Surface coating of A has the first carbon-coating.By
In LiM1PO4For semi-conducting material, for improving its electric conductivity, the Surface coating at A has the first carbon-coating.
In the present invention one preferred implementation, when A is LiM2O2Or LiM3 2O4Time, the surface of A can be wrapped
Cover the first carbon-coating.Due to LiM2O2Or LiM3 2O4For conductor material, not being coated with the first carbon-coating, electric conductivity is also
Preferably.
In the present invention one preferred implementation, when A is LiM1PO4Time, the Surface coating of A has the first carbon-coating, with
Time LiC6Surface coating has the second carbon-coating, is also wrapped on the 3rd on the surface on the surface of the first carbon-coating and the second carbon-coating
Carbon-coating, comprise Surface coating in the 3rd carbon-coating has the LiM of the first carbon-coating simultaneously1PO4The second carbon is had with Surface coating
The LiC of layer6.By so arranging, LiM1PO4Electric conductivity relatively strong, and LiC6After Fu He, do not affecting
LiM1PO4Electric conductivity on the premise of, improve LiM1PO4Capacity.
In the present invention one preferred implementation, the material of carbon-coating is Delanium, native graphite, acetylene black, charcoal
In black, carbonaceous mesophase spherules, CNT, carbon nano-fiber, Graphene, superconduction white carbon black and superconduction carbon fiber
At least one.
LiCoO2、LiMn2O4Or LiFePO4Relatively low etc. the capacity of traditional battery anode active material, and compacting
Density is relatively low, it is difficult to obtain the battery of high-energy-density；Traditional LiC6Capacity be 339mAh/g, although hold
Measure higher, but LiC6Electric conductivity and less stable, it is impossible to separately as positive electrode active materials use.This
Invention is by LiM1PO4、LiM2O2And LiM3 2O4In at least one and LiC6Be combined, obtained a kind of newly
Anode active material of lithium ion battery (A)1-x·(LiC6)x, in this anode active material of lithium ion battery, LiC6
Uniformly it is embedded in the crystalline structure of A and/or LiC6And forming chemical bond between A, both are not simple solid
The relation mixed mutually.LiC6After compound with A, LiC6The lithium of abundance is provided so that lithium for positive electrode active materials
Ion battery positive electrode active materials capacity is greatly improved, and range of capacity is 170-339mAh/g, and can be according to x
Change adjust anode active material of lithium ion battery capacity.It addition, anode active material of lithium ion battery
Compacted density also improves a lot, thus improves the energy density of lithium ion battery.Meanwhile, lithium-ion electric
The stability of pond positive electrode active materials is preferable, electric conductivity is good, the lithium ion cell positive activity that the present invention obtains
The overall performance of material is better than single A battery anode active material and single LiC6Battery positive electrode active material
Material.
The capacity of the anode active material of lithium ion battery that first aspect present invention provides is higher, it addition, lithium ion
The good stability of battery anode active material, electric conductivity is preferable.
Second aspect present invention provides the preparation method of a kind of anode active material of lithium ion battery, including following
Step:
A presoma is provided；A is LiM1PO4、LiM2O2And LiM3 2O4In at least one, M1、M2Or
M3Selected from at least one in ferrum, cobalt, manganese, nickel, aluminum and vanadium, in protective gas or air, by A
Presoma, after 200-500 DEG C of constant temperature pre-burning 1-5h, is naturally cooling to room temperature, obtains the A presoma after pre-burning；
LiC is provided6Presoma；
By the A presoma after pre-burning and LiC6After presoma is 1-x:x mix homogeneously according to mol ratio, obtain lithium from
Sub-battery anode active material presoma, 0 < x < 1, then in protective gas, by lithium ion cell positive
Active material presoma is Isothermal sinter 5min-2h at 300-700 DEG C, obtains anode active material of lithium ion battery,
The chemical formula of anode active material of lithium ion battery is (A)1-x·(LiC6)x, 0 < x < 1.
In embodiment of the present invention, the preparation method of A presoma can be existing conventional method, such as high temperature solid-state
Reducing process, sol-gel process, hydro-thermal method or microwave method.
In the present invention one preferred implementation, A is LiCoO2、LiMn2O4Or LiFePO4。
In the present invention one preferred implementation, LiFePO4The preparation method of presoma is:
Lithium source, source of iron and the phosphorus source ratio with mol ratio as 1:1:1 is dissolved in solvent respectively, obtains mixing molten
Liquid, is heated to 40-60 DEG C by mixed solution, reacts 10-100min, after question response terminates, is entered by mixed solution
Row is spray-dried, and obtains nanoscale LiFePO4Presoma.
In the present invention one preferred implementation, lithium source is lithium oxide, Lithium hydrate, Quilonorm (SKB), lithium carbonate, nitre
At least one in acid lithium, lithium nitrite, lithium phosphate, lithium dihydrogen phosphate, lithium oxalate, lithium molybdate and lithium vanadate.
In the present invention one preferred implementation, source of iron is iron phosphate, ferrous phosphate, Ferrous acetate, pyrophosphoric acid Asia
Ferrum, ferrous carbonate, ferrous chloride, ferrous hydroxide, ferrous nitrate, Ferrox., iron chloride, hydroxide
At least one in ferrum, ferric nitrate, ferric citrate and iron sesquioxide.
In the present invention one preferred implementation, phosphorus source is phosphoric acid, diammonium phosphate, iron phosphate and lithium dihydrogen phosphate
In at least one.
In the present invention one preferred implementation, solvent be water, ethanol, acetone, propanol, isopropanol, isobutanol,
Methanol, n-butyl alcohol, acetonitrile, oxolane, ether, dichloromethane, chloroform, dimethyl sulfoxide and dimethyl methyl
At least one in amide.
In the present invention one preferred implementation, by the LiH of 1mol2PO4It is dissolved in the water, forms LiH2PO4Solution,
After the fe of 1mol is positioned in glacial acetic acid, with LiH2PO4Solution mixes, and obtains mixed solution.
Wherein, the acting as reacting with Fe of glacial acetic acid forms it into iron liquor, additionally can also be as iron ion
Compound and LiH2PO4The catalyst forming ferric lithium phosphate precursor reaction uses.The preparation side of this mixed solution
Method is simple, unique.
In the present invention one preferred implementation, in protective gas, at a temperature of 150-400 DEG C, will mix molten
Liquid is spray-dried.
In the present invention one preferred implementation, protective gas is at least one in nitrogen, argon and helium.
The present invention is after providing A presoma, by A presoma in protective gas or air, and 200-500 DEG C of perseverance
After temperature pre-burning 1-5h, it is naturally cooling to room temperature；By pre-burning, in A presoma, lattice portion is formed, now shape
Become semi-finished product, follow-up by the A presoma after pre-burning and LiC6Presoma proceeds sintering, the temperature now sintered
Degree is not required to Tai Gao and sintering time be not required to oversize can be by A presoma and LiC6Presoma fully sinters, it is to avoid
LiC under high temperature6The problem of presoma volatilization, and obtained the lithium ion cell positive that sintering is abundant, lattice is good
Active material.
In the present invention one preferred implementation, when A is LiM1PO4Time, protective gas carries out pre-burning.?
In protective gas, the purpose of pre-burning is to prevent LiM1PO4The oxidation of submetallic ion.
In the present invention one preferred implementation, protective gas is at least one in nitrogen, argon and helium.
In the present invention one preferred implementation, when A is LiM2O2Or LiM3 2O4Time, carry out pre-burning in atmosphere.
In the present invention one preferred implementation, add material with carbon element when preparing A presoma, with at A forerunner's body surface
Bread covers the first carbon-coating.
In the present invention one preferred implementation, material with carbon element is conductive carbon or organic carbon source, conductive carbon be Delanium,
Native graphite, acetylene black, white carbon black, carbonaceous mesophase spherules, CNT, carbon nano-fiber, Graphene, super
Lead at least one in white carbon black and superconduction carbon fiber；Organic carbon source is phenolic resin, polyvinyl alcohol, Colophonium and sugarcane
At least one in sugar.
In the present invention one preferred implementation, add material with carbon element when A presoma pre-burning.
In the present invention one preferred implementation, after A presoma and material with carbon element being mixed, then carry out constant temperature pre-burning,
Obtain Surface coating and have the A presoma of the first carbon-coating.
In embodiment of the present invention, the addition of material with carbon element is that industry routine selects, and does not the most do particular determination.
In embodiment of the present invention, when A presoma is LiM2O2And LiM3 2O4Time, the particle diameter of A presoma is normal
Rule select.
In embodiment of the present invention, when A presoma is LiM1PO4Time, the particle diameter of A presoma is conventional selection.
In embodiment of the present invention, LiC6The preparation method of presoma is: provide with C as negative electrode, with Li as sun
Pole, closes arsenic (V) with lithium hexafluoro phosphate, tetraethylammonium tetrafluoroborate, LiBF4, lithium perchlorate, hexafluoro
Acid lithium, trifluoromethanesulfonic acid lithium, form solid polymer, gelatin polymer or bis trifluoromethyl sulfimide lithium are
Electrolyte electrochemical battery, in protective gas, applies the voltage of 0.5-2.5V, makes to electrochemical cell
The Li ionized out from anode+It is deposited on negative electrode C, obtains LiC6Presoma.
In embodiment of the present invention, by post-depositional negative electrode 40-100 DEG C of drying, LiC under vacuum6Forerunner
Body strips down from negative electrode and carries out ball milling or sand milling, obtains nano level LiC6Presoma.
In embodiment of the present invention, at nano level LiC6Presoma Surface coating the second carbon-coating.
In embodiment of the present invention, by nano level LiC6After presoma mixes with material with carbon element, at protective gas
In, sinter 5-10min at 40-300 DEG C, obtaining Surface coating has the LiC of the second carbon-coating6Presoma.
In embodiment of the present invention, material with carbon element is conductive carbon or organic carbon source, and conductive carbon is Delanium, natural
Graphite, acetylene black, white carbon black, carbonaceous mesophase spherules, CNT, carbon nano-fiber, Graphene, superconduction charcoal
At least one in black and superconduction carbon fiber；Organic carbon source is in phenolic resin, polyvinyl alcohol, Colophonium and sucrose
At least one.
In embodiment of the present invention, LiC6The Surface coating of presoma has carbon-coating, can improve by so arranging
LiC6The electric conductivity of presoma.
In embodiment of the present invention, LiC6The particle diameter of presoma is 10-80nm.
The present invention uses electrochemical deposition method to prepare LiC6Presoma, after applying voltage to electrochemical cell,
Li anode ionizes out Li+, Li+Through bath deposition on negative electrode C, obtain LiC6Presoma, this preparation side
Method is simple, effective, and the LiC obtained6Presoma particle diameter is nanoscale.
When the particle diameter of A presoma is nanoscale, LiC6When persursor material is nanoscale, in sintering process,
A presoma and LiC6Presoma assemble formed eutectic, obtain anode active material of lithium ion battery, this lithium from
Capacity and the compacted density of sub-battery anode active material are the highest.
When the particle diameter of A presoma is micron order, LiC6When persursor material is nanoscale, formed through oversintering
Eutectic, particle diameter becomes big, obtains micron-sized anode active material of lithium ion battery, this lithium ion cell positive
Capacity and the compacted density of active material are the highest.
In embodiment of the present invention, by the concrete operations that anode active material of lithium ion battery presoma sinters it is:
Anode active material of lithium ion battery presoma is warming up to 400-600 DEG C with the heating rate of 1-5 DEG C/min, permanent
After temperature sintering 5-10min, it is down to room temperature with the rate of temperature fall of 1-5 DEG C/min.
The sintering temperature of the present invention is relatively low, can avoid LiC in sintering process6Volatilization.It addition, 1-5 DEG C/min
Heating rate when being warming up to 400-600 DEG C, contribute to the shape of anode active material of lithium ion battery presoma lattice
Becoming, be down to room temperature with the rate of temperature fall of 1-5 DEG C/min, rate of temperature fall is relatively slow, contributes to forming the crystalline substance that crystal formation is good
Body.
In embodiment of the present invention, the sintering overall process of the present invention is all carried out, in constant temperature oven in sintering process
Any Equipment for Heating Processing that uniformly can heat under atmosphere protection all can use, such as vacuum drying oven, batch-type furnace, tunnel
Stove, rotary atmosphere furnace, clock hood type furnace, tube furnace, shuttle-type stove or pushed bat kiln etc..
In embodiment of the present invention, protective gas is at least one in nitrogen, argon and helium.
In embodiment of the present invention, by the A presoma after pre-burning and LiC6The method of presoma mix homogeneously can be
Stirring, ultrasonic, ball milling, sand milling or high speed dispersion, it is only necessary to by the A presoma after pre-burning and LiC6Presoma
Mix homogeneously, concrete mode is not particularly limited.
In embodiment of the present invention, by the A presoma after pre-burning and LiC6After presoma mix homogeneously, add carbon
Material, obtains anode active material of lithium ion battery presoma, then in protective gas, at 300-700 DEG C
Lower Isothermal sinter 5min-2h, the anode active material of lithium ion battery Surface coating obtained has the 3rd carbon-coating.Here
Refer to A surface and LiC in the anode active material of lithium ion battery obtained6Surface coating has the 3rd carbon-coating, should
Comprise A and LiC in 3rd carbon-coating simultaneously6。
In embodiment of the present invention, by LiC6Surface coating after presoma and pre-burning has the A forerunner of the first carbon-coating
After body mix homogeneously, add material with carbon element, obtain anode active material of lithium ion battery presoma, then in protection
In property gas, Isothermal sinter 5min-2h at 300-700 DEG C, the anode active material of lithium ion battery table obtained
Bread is covered with the 3rd carbon-coating.Comprise LiC in 3rd carbon-coating simultaneously6With the A that Surface coating has the first carbon-coating.
In embodiment of the present invention, the A presoma after pre-burning and Surface coating are had the LiC of the second carbon-coating6Forerunner
After body mix homogeneously, add material with carbon element, obtain anode active material of lithium ion battery presoma, then in protection
In property gas, Isothermal sinter 5min-2h at 300-700 DEG C, the anode active material of lithium ion battery table obtained
Bread is covered with the 3rd carbon-coating.Comprise A in 3rd carbon-coating simultaneously and Surface coating has the LiC of the second carbon-coating6。
In embodiment of the present invention, the Surface coating after pre-burning is had A presoma and the Surface coating of the first carbon-coating
There is the LiC of the second carbon-coating6After presoma mix homogeneously, add material with carbon element, obtain lithium ion cell positive activity material
Material precursor, then in protective gas, Isothermal sinter 5min-2h at 300-700 DEG C, the lithium obtained from
Sub-battery anode active material Surface coating has the 3rd carbon-coating.Comprise Surface coating in 3rd carbon-coating simultaneously and have first
The A of carbon-coating and Surface coating have the LiC of the second carbon-coating6。
In embodiment of the present invention, 0.01≤x≤0.6.
In embodiment of the present invention, 0.05≤x≤0.4, as 0.05≤x≤0.4, A and LiC6There is applicable ratio,
Stability that positive electrode active materials had and more preferable chemical property can be made.
In embodiment of the present invention, 0.1≤x≤0.2.
In embodiment of the present invention, when A is LiM1PO4Time, the particle diameter of anode active material of lithium ion battery is for receiving
Meter level or micron order, compacted density is 2.3-2.5g/cm3。
In embodiment of the present invention, when A is LiM2O2Or LiM3 2O4Time, anode active material of lithium ion battery
Particle diameter is micron order, and compacted density is 3.9-4.2g/cm3。
The preparation method of a kind of anode active material of lithium ion battery that embodiment of the present invention second aspect provides, logical
A presoma after crossing pre-burning and LiC6Presoma mixes to be incorporated under certain temperature and time and is sintered,
Sintering time is shorter, and method is simple, unique, effective, can make LiC6Uniformly it is embedded in the crystal formation knot of A
In structure and/or LiC6And forming chemical bond between A, prepared anode active material of lithium ion battery capacity is higher,
It addition, the good stability of anode active material of lithium ion battery, electric conductivity is preferable.
Third aspect present invention provides a kind of lithium ion battery, and this lithium ion battery comprises the embodiment of the present invention the
On the one hand the anode active material of lithium ion battery provided.
Lithium ion battery includes anode pole piece, cathode pole piece, barrier film, electrolyte and shell, wherein, positive pole pole
Anode active material of lithium ion battery, conductive agent and the binding agent that sheet is provided by collector, first aspect present invention
Composition.
In embodiment of the present invention, collector is aluminium foil, nickel screen or aluminum-plastic composite membrane.
In embodiment of the present invention, conductive agent is acetylene black.
In embodiment of the present invention, binding agent is Kynoar (PVDF), butadiene-styrene rubber breast (SBR) or carboxylic
Sodium carboxymethylcellulose pyce (CMC).
Cathode pole piece, barrier film, electrolyte and shell be chosen as industry prior art, the most do not do particular determination.
The lithium ion battery that the embodiment of the present invention third aspect provides has excellent discharge capacity, and energy density is relatively
Height, cycle performance is preferable.
Embodiment 1:
The preparation method of a kind of anode active material of lithium ion battery, comprises the following steps:
(1) LiFePO is prepared4Presoma
By the LiH of 1mol2PO4It is dissolved in the water, forms LiH2PO4Solution, is positioned over ice by the fe of 1mol
After acetic acid, with LiH2PO4Solution mixes, and obtains mixed solution, mixed solution is heated to 40 DEG C, instead
Answer 100min, question response to be spray-dried after terminating, obtain nanoscale LiFePO4Presoma；In argon gas
In, by LiFePO4After presoma and Delanium mixing, after 200 DEG C of constant temperature pre-burning 5h, it is naturally cooling to room
Temperature, obtains the A presoma after pre-burning；A presoma Surface coating after this pre-burning has the first carbon-coating；
(2) LiC is prepared6Presoma
There is provided with C as negative electrode, Li is as anode, lithium hexafluoro phosphate is as electrolyte electrochemical cell, at argon gas
In body, apply the voltage of 0.5-2.5V to electrochemical cell, make to ionize out from anode Li+It is deposited on negative electrode
On C, by the 40 DEG C of drying under vacuum of post-depositional negative electrode, by LiC6Presoma strips down from negative electrode,
Then carry out ball milling, obtain nano level LiC6Presoma, by nano level LiC6Presoma mixes with Delanium
After conjunction, in protective gas, sintering 6min at 100 DEG C, obtaining Surface coating has the LiC of the second carbon-coating6Before
Drive body.
(3) (LiFePO is prepared4)1-x·(LiC6)x
A presoma after pre-burning and Surface coating are had the LiC of the second carbon-coating6Presoma according to mol ratio is
After 0.9:0.1 mix homogeneously, obtain anode active material of lithium ion battery presoma, then in argon gas,
Anode active material of lithium ion battery presoma is warming up to 400 DEG C with the heating rate of 1 DEG C/min, Isothermal sinter
After 10min, it is down to room temperature with the rate of temperature fall of 1 DEG C/min, obtains anode active material of lithium ion battery
(LiFePO4)0.9·(LiC6)0.1。
The preparation method of lithium ion battery
By 800 grams of anode active material of lithium ion battery (LiFePO prepared according to the method described above4)0.9·(LiC6)0.1、
100 grams of conductive agent acetylene blacks, 100 grams of binding agent Kynoar (PVDF), join 800 grams of N-methyl
In pyrrolidone solution (nmp solution), de-airing mixer stirs 2h, prepares anode sizing agent；
This anode sizing agent is coated on aluminium foil uniformly, through 110 DEG C of drying, cuts into a size of after rolling
93*122mm positive plate.
By 920 grams of negative active core-shell material native graphites, 30 grams of binding agent butadiene-styrene rubber breast (SBR), 30 grams of carboxylic first
Base sodium cellulosate (CMC) joins in 500 grams of water, stirs 2h in de-airing mixer, prepares negative pole slurry
Material, is uniformly coated to cathode size on Copper Foil, obtains lithium ion battery negative through 120 DEG C of drying, rollings
Pole piece.
Using commercial electrolytic liquid, electrolyte includes ethylene carbonate, LiPF6And organic solvent.
Anode slice of lithium ion battery, lithium ion battery negative electrode and the barrier film that will prepare in the present embodiment 1
Successively by the battery core of up-coiler stacking wound into rolls, the battery core obtained is put in the housing of one end open, note
Enter the electrolyte prepared in the present embodiment 1, after sealing, make lithium ion battery.
The anode active material of lithium ion battery that embodiment 1 prepares is carried out XRD test, test result such as Fig. 2 institute
Showing, Fig. 2 is XRD (X-ray diffraction) figure of the anode active material of lithium ion battery that the embodiment of the present invention prepares；
From figure 1 it appears that the anode active material of lithium ion battery that the embodiment of the present invention 1 prepares
(LiFePO4)0.9·(LiC6)0.1X-ray diffraction peak intensity big, sharp-pointed, the lithium ion cell positive work prepared be described
Property material there is good crystallinity, test comparison standard PDF card, find this lithium ion cell positive activity
Material has LiFePO simultaneously4(representing with LFP in figure) and LiC6Characteristic spectrum, illustrate what the present invention obtained
Anode active material of lithium ion battery is by LiFePO4And LiC6It is composited.It addition, LiFePO4Crystal formation not
Change.By calculating, LiFePO in anode active material of lithium ion battery4And LiC6Shared mol ratio is about
0.9:0.1。
The lithium ion battery prepared by above-described embodiment 1, in the voltage range of 2.0-3.8V, carries out charge and discharge electrical measurement
Examination, result is as it is shown on figure 3, charging and discharging curve figure that Fig. 3 is the lithium ion battery that the embodiment of the present invention 1 prepares；
From figure 3, it can be seen that the electric discharge gram volume of this lithium ion battery 0.2C is up to 175mAh/g, calculates and fill first
Discharging efficiency, the discharge capacity/initial charge capacity of first charge-discharge efficiency=first.It is calculated the head of this battery
Secondary efficiency for charge-discharge reaches 99.4%.The gram volume of the battery anode active material that the present invention provides is high, and electric discharge is flat
Platform is stable, superior performance.
The lithium ion battery that embodiment 1 prepares is circulated performance test, and charge and discharge voltage is 2.0-3.8V, test
As shown in Figure 4, Fig. 4 is the cycle performance figure of the lithium ion battery that the embodiment of the present invention 1 prepares to result；From Fig. 4
It can be seen that use (LiFePO4)0.9·(Li2C)0.1The lithium ion battery made as positive electrode active materials is at 1.0C
The cycle performance curve chart of discharge and recharge, it can be seen that 1C 100 capability retentions of circulation are 99.9%,
Cycle performance is good.
Fig. 5 be the lithium ion battery for preparing of the embodiment of the present invention 1 different multiplying power (discharge-rate be respectively 1.0C,
1.5C, 2.0C, 2.5C, 3.0C) under cycle performance figure.Result is as shown in Figure 5.From fig. 5, it can be seen that 1.0C
Under multiplying power during electric discharge, electric discharge gram volume is 168mAh/g first, and the gram volume that discharges after circulating 4 times is still
168mAh/g.Under 1.5C multiplying power during electric discharge, electric discharge gram volume is 164mAh/g first, electric discharge gram after circulating 4 times
Capacity is still 164mAh/g.Under 2.0C multiplying power during electric discharge, electric discharge gram volume is 160mAh/g first, circulates 4 times
Rear electric discharge gram volume is still 160mAh/g.Under 2.5C multiplying power during electric discharge, electric discharge gram volume is 156mAh/g first,
The gram volume that discharges after circulating 4 times is still 156mAh/g.Under 3.0C multiplying power during discharge and recharge, electric discharge gram volume is first
154mAh/g, the gram volume that discharges after circulating 4 times is still 154mAh/g.3.0C capacity is the 91.6% of 1.0C capacity.
After circulating 22 times, the electric discharge gram volume under 1.0C, close to 168mAh/g, illustrates the lithium that the embodiment of the present invention 1 prepares
Ion battery positive electrode active materials discharge performance under different multiplying powers is good, and capacity is higher and cycle performance is good
Good, thus show the anode active material of lithium ion battery using the embodiment of the present invention to prepare
(LiFePO4)1-x·(LiC6)xThe battery that high power capacity, high magnification and cycle performance are good can be assembled into.
Embodiment 2:
The preparation method of a kind of anode active material of lithium ion battery, comprises the following steps:
(1) LiFePO is prepared4Presoma
By the LiH of 1mol2PO4It is dissolved in the water, forms LiFePO4Solution, is positioned over ice by the fe of 1mol
After acetic acid, with LiH2PO4Solution mixes, and obtains mixed solution, mixed solution is heated to 40 DEG C, instead
Answer 100min, question response to be spray-dried after terminating, obtain nanoscale LiFePO4Presoma；In argon gas
In, by LiFePO4After presoma and Delanium mixing, after 500 DEG C of constant temperature pre-burning 1h, it is naturally cooling to room
Temperature, obtains the A presoma after pre-burning；A presoma Surface coating after this pre-burning has the first carbon-coating；
(2) LiC is prepared6Presoma
There is provided with C as negative electrode, Li is as anode, lithium hexafluoro phosphate is as electrolyte electrochemical cell, at argon gas
In body, apply the voltage of 0.5-2.5V to electrochemical cell, make the Li ionized out in anode+It is deposited on negative electrode C,
By the 100 DEG C of drying under vacuum of post-depositional negative electrode, by LiC6Presoma strips down from negative electrode, then
Carry out ball milling, obtain nano level LiC6Presoma, by nano level LiC6After presoma mixes with Delanium,
In argon gas, sintering 5min at 300 DEG C, obtaining Surface coating has the LiC of the second carbon-coating6Presoma.
(3) (LiFePO is prepared4)1-x·(LiC6)x
A presoma after pre-burning and Surface coating are had the LiC of the second carbon-coating6Presoma according to mol ratio is
After 0.95:0.05 mix homogeneously, add Delanium, mixing, obtain anode active material of lithium ion battery forerunner
Body, then in argon gas, by anode active material of lithium ion battery presoma with the heating rate of 5 DEG C/min
It is warming up to 600 DEG C, after Isothermal sinter 5min, is down to room temperature with the rate of temperature fall of 5 DEG C/min, obtains lithium-ion electric
Pond positive electrode active materials (LiFePO4)0.95·(LiC6)0.05.This anode active material of lithium ion battery Surface coating has
Three carbon-coatings.
The preparation method of lithium ion battery is with embodiment 1.
Embodiment 3:
The preparation method of a kind of anode active material of lithium ion battery, comprises the following steps:
(1) LiFePO is prepared4Presoma
By the LiH of 1mol2PO4It is dissolved in the water, forms LiH2PO4Solution, is positioned over ice by the fe of 1mol
After acetic acid, with LiH2PO4Solution mixes, and obtains mixed solution, mixed solution is heated to 40 DEG C, instead
Answer 100min, question response to be spray-dried after terminating, obtain nanoscale LiFePO4Presoma；In argon gas
In, by LiFePO4Presoma, after 300 DEG C of constant temperature pre-burning 2h, is naturally cooling to room temperature, obtains the A after pre-burning
Presoma；
(2) LiC is prepared6Presoma
There is provided with C as negative electrode, Li is as anode, lithium hexafluoro phosphate is as electrolyte electrochemical cell, at argon gas
In body, apply the voltage of 0.5-2.5V to electrochemical cell, make the Li ionized out from anode+It is deposited on negative electrode C
On, by the 100 DEG C of drying under vacuum of post-depositional negative electrode, by LiC6Presoma strips down from negative electrode,
Then carry out ball milling, obtain nano level LiC6Presoma.
(3) (LiFePO is prepared4)1-x·(LiC6)x
By the A presoma after pre-burning and LiC6After presoma is 0.6:0.4 mix homogeneously according to mol ratio, obtain lithium from
Sub-battery anode active material presoma, then in argon gas, before anode active material of lithium ion battery
Drive body and be warming up to 500 DEG C with the heating rate of 3 DEG C/min, after Isothermal sinter 8min, with the rate of temperature fall of 3 DEG C/min
It is down to room temperature, obtains anode active material of lithium ion battery (LiFePO4)0.6·(LiC6)0.4。
The preparation method of lithium ion battery is with embodiment 1.
Embodiment 4:
The preparation method of a kind of anode active material of lithium ion battery, comprises the following steps:
(1) LiCoO is prepared2Presoma
Lithium carbonate and cobalt carbonate are mixed according to the ratio that mol ratio is 1:1, the most in atmosphere 900 DEG C of heating 5h,
Micron order LiCoO is formed by solid-phase synthesis2Presoma；In atmosphere, by LiCoO2Presoma and artificial stone
After ink mixing, after 300 DEG C of constant temperature pre-burning 2h, it is naturally cooling to room temperature, obtains the A presoma after pre-burning；In advance
A presoma Surface coating after burning has the first carbon-coating；
(2) LiC is prepared6Presoma
There is provided with C as negative electrode, Li is as anode, lithium hexafluoro phosphate is as electrolyte electrochemical cell, at argon gas
In body, apply the voltage of 0.5-2.5V to electrochemical cell, make the Li ionized out from anode+It is deposited on negative electrode C
On, by the 100 DEG C of drying under vacuum of post-depositional negative electrode, by LiC6Presoma strips down from negative electrode,
Then carry out ball milling, obtain nano level LiC6Presoma, by nano level LiC6Presoma mixes with Delanium
After conjunction, in argon gas, sintering 6min at 200 DEG C, obtaining Surface coating has the LiC of the second carbon-coating6Forerunner
Body.
(3) (LiCoO is prepared2)1-x·(LiC6)x
By being coated with the A presoma of the first carbon-coating and being coated with the LiC of the second carbon-coating after pre-burning6Presoma according to
After mol ratio is 0.6:0.4 mix homogeneously, adds Delanium, mixing, obtain lithium ion cell positive activity material
Material precursor, then in argon gas, by anode active material of lithium ion battery presoma with the liter of 3 DEG C/min
Temperature ramp, to 500 DEG C, after Isothermal sinter 8min, is down to room temperature with the rate of temperature fall of 3 DEG C/min, is obtained lithium
Ion battery positive electrode active materials (LiCoO2)0.6·(LiC6)0.4.This anode active material of lithium ion battery surface is wrapped
It is covered with the 3rd carbon-coating.
The preparation method of lithium ion battery is with embodiment 1.
Embodiment 5:
The preparation method of a kind of anode active material of lithium ion battery, comprises the following steps:
(1) LiMn is prepared2O4Presoma
By LiMn2O4Stoichiometric proportion weigh lithium carbonate and electrolytic manganese dioxide, grind and make both mix homogeneously,
After 100 DEG C of dry 2h, under 850 DEG C of air atmospheres, sinter 12h, prepare micron order LiMn2O4Presoma；?
In air, by LiMn2O4After presoma and Delanium mixing, after 300 DEG C of constant temperature pre-burning 2h, Temperature fall
To room temperature, obtain the A presoma after pre-burning；A presoma Surface coating after pre-burning has the first carbon-coating；
(2) LiC is prepared6Presoma
There is provided with C as negative electrode, Li is as anode, lithium hexafluoro phosphate is as electrolyte electrochemical cell, at argon gas
In body, apply the voltage of 0.5-2.5V to electrochemical cell, make the Li ionized out from anode+It is deposited on negative electrode C
On, by post-depositional negative electrode 100 DEG C of drying, LiC under vacuum6Presoma strips down from negative electrode, so
After carry out ball milling, obtain nano level LiC6Presoma, by nano level LiC6Presoma mixes with Delanium
After, in argon gas, sinter 10min at 40 DEG C, obtaining Surface coating has the LiC of the second carbon-coating6Presoma.
(3) (LiMn is prepared2O4)1-x·(LiC6)x
A presoma after pre-burning and Surface coating are had the LiC of the second carbon-coating6Presoma according to mol ratio is
After 0.6:0.4 mix homogeneously, add Delanium, mixing, obtain anode active material of lithium ion battery presoma,
Then, in argon gas, anode active material of lithium ion battery presoma is heated up with the heating rate of 3 DEG C/min
To 500 DEG C, after Isothermal sinter 8min, it is down to room temperature with the rate of temperature fall of 3 DEG C/min, just obtains lithium ion battery
Pole active material (LiMn2O4)0.6(LiC6)0.4.This anode active material of lithium ion battery Surface coating has the 3rd carbon
Layer.
The preparation method of lithium ion battery is with embodiment 1.
Comparative example 1
Use independent LiFePO4、LiCoO2、LiMn2O4Material, as positive electrode active materials, uses and implements
The manufacture method that example one is identical, makes electrode and lithium ion battery.
Comparative example 2
By LiFePO4And LiC6Carrying out simple physical mixed and such as stir mixing, the mixing material obtained is as just
Pole active material, uses the manufacture method identical with embodiment one, makes electrode and lithium ion battery.
Battery and comparative example 1-2 of above-described embodiment 1 are carried out performance comparison, and comparing result is as shown in the table.
Table 1 lithium ion battery of the present invention and the capacity of comparative example 1 lithium ion battery and energy density compare
| Lithium ion battery (0 < x < 1) | Peak capacity enhancing rate | Highest energy density enhancing rate |
| Positive electrode active materials (LiFePO4)1-x·(LiC6)x | 25% | 25% |
| Positive electrode active materials (LiCoO2)1-x·(LiC6)x | 20% | 20% |
| Positive electrode active materials (LiMn2O4)1-x·(LiC6)x | 20% | 20% |
Table 1 is lithium ion battery of the present invention and the capacity of comparative example 1 lithium ion battery and energy density compares, from
It can be seen that relative to the single LiFePO of comparative example 1 in table 14, positive electrode active materials of the present invention is
(LiFePO4)1-x·(LiC6)xThe capacity of lithium ion battery the highest improve 25%, energy density is the highest also to be improved
25%.Relative to the single LiCoO of comparative example 12, positive electrode active materials of the present invention is (LiCoO2)1-x·(LiC6)x
The capacity of lithium ion battery the highest improve 20%, energy density is the highest also improves 20%.Relative to contrast
The single LiMn of example 12O4, positive electrode active materials of the present invention is (LiMn2O4)1-x·(LiC6)xLithium ion battery
Capacity is the highest improves 20%, and energy density is the highest also improves 20%.Relative to comparative example 1, above lithium
Average size enhancing rate and the mean energy density enhancing rate of ion battery are more than 10%.Require emphasis
It is, the most only with (LiFePO4)1-x·(LiC6)x、(LiCoO2)1-x·(LiC6)x, and (LiMn2O4)1-x·(LiC6)xAs a example by,
Capacity and the energy of the lithium ion battery that other anode active material of lithium ion battery of present invention protection are made are close
Spending the positive electrode active materials conventional compared to prior art, capacity and energy density the most all substantially increase.
Table 2 is the embodiment of the present invention 1 prepared lithium ion battery and the capacity of comparative example 1-2, energy density and circulation
The comparison of performance
As can be seen from Table 2, the pure LiFePO and in comparative example 14The lithium prepared as positive electrode active materials from
Sub-battery is compared, and the anode active material of lithium ion battery that the embodiment of the present invention 1 provides can make lithium ion battery energy
Metric density and capacity are obtained for certain lifting.Therefore, the lithium ion battery that the embodiment of the present invention 1 provides is just
Pole active material can make lithium ion battery have higher energy density.
With the LiFePO in comparative example 24And LiC6The lithium prepared as positive electrode active materials of physical mixed material
Ion battery is compared, and the anode active material of lithium ion battery that the embodiment of the present invention 1 provides can make lithium ion battery
Capacity, energy density and cycle performance be all greatly increased.Illustrate that positive electrode active materials that the present invention prepares is not
It is LiFePO4And LiC6Simple physical mixing.
To sum up, the anode active material of lithium ion battery that the embodiment of the present invention provides, by common positive-active
Material adds LiC6, improve the energy density of lithium ion battery, make lithium ion battery of the present invention extensively to apply
In energy storage field.Meanwhile, the cycle performance of this anode active material of lithium ion battery is preferable, and stability is higher.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed,
But therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that, for this area
For those of ordinary skill, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement,
These broadly fall into protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be with claims
It is as the criterion.
Claims (10)
1. an anode active material of lithium ion battery, it is characterised in that described lithium ion cell positive activity
The chemical expression of material is (A)1-x·(LiC6)x, wherein, 0 < x < 1, A is LiM1PO4、LiM2O2With
LiM3 2O4In at least one, M1、M2Or M3Selected from in ferrum, cobalt, manganese, nickel, aluminum and vanadium at least
A kind of.
2. anode active material of lithium ion battery as claimed in claim 1, it is characterised in that described x takes
Value scope is 0.05≤x≤0.4.
3. anode active material of lithium ion battery as claimed in claim 1, it is characterised in that the table of described A
Bread is covered with the first carbon-coating or described LiC6Surface coating have the Surface coating of the second carbon-coating or described A to have
The one the most described LiC of carbon-coating6Surface coating have the second carbon-coating.
4. anode active material of lithium ion battery as claimed in claim 3, it is characterised in that when described A's
When Surface coating has the first carbon-coating, the surface of described first carbon-coating and described LiC6Surface be also wrapped on the 3rd carbon
Layer, comprises described LiC in described 3rd carbon-coating simultaneously6With the A that Surface coating has the first carbon-coating；
As described LiC6Surface coating when having the second carbon-coating, the surface of described A and the surface of described second carbon-coating
It is also wrapped on the 3rd carbon-coating, comprises A in described 3rd carbon-coating simultaneously and Surface coating has the LiC of the second carbon-coating6；
When the Surface coating of described A has the first the most described LiC of carbon-coating6Surface coating when having the second carbon-coating, institute
The surface on the surface and described second carbon-coating of stating the first carbon-coating is also wrapped on the 3rd carbon-coating, in described 3rd carbon-coating
Comprise Surface coating has the A of the first carbon-coating and Surface coating to have the LiC of the second carbon-coating simultaneously6。
5. the preparation method of an anode active material of lithium ion battery, it is characterised in that comprise the following steps:
A presoma is provided；Described A is LiM1PO4、LiM2O2And LiM3 2O4In at least one, M1、
M2Or M3Selected from at least one in ferrum, cobalt, manganese, nickel, aluminum and vanadium, in protective gas or air,
By described A presoma after 200-500 DEG C of constant temperature pre-burning 1-5h, it is naturally cooling to room temperature, obtains the A after pre-burning
Presoma；
LiC is provided6Presoma；
By the A presoma after described pre-burning and described LiC6After presoma is 1-x:x mix homogeneously according to mol ratio,
Obtain anode active material of lithium ion battery presoma, 0 < x < 1, then in protective gas, by described lithium
Ion battery positive electrode active materials presoma Isothermal sinter 5min-2h at 300-700 DEG C, obtains lithium ion battery
Positive electrode active materials, the chemical formula of described anode active material of lithium ion battery is (A)1-x·(LiC6)x, 0 < x < 1.
6. the preparation method of anode active material of lithium ion battery as claimed in claim 5, it is characterised in that
By the concrete operations that described anode active material of lithium ion battery presoma sinters it is: by described lithium ion battery
Positive electrode active materials presoma is warming up to 400-600 DEG C with the heating rate of 1-5 DEG C/min, Isothermal sinter 5-10min
After, it is down to room temperature with the rate of temperature fall of 1-5 DEG C/min.
7. the preparation method of anode active material of lithium ion battery as claimed in claim 5, it is characterised in that
Described LiC6The preparation method of presoma is: provide with C as negative electrode, with Li as anode, with lithium hexafluoro phosphate,
Tetraethylammonium tetrafluoroborate, LiBF4, lithium perchlorate, hexafluoro close arsenic (V) acid lithium, trifluoromethanesulfonic acid lithium,
Form solid polymer, gelatin polymer or bis trifluoromethyl sulfimide lithium are electrolyte electrochemical battery,
In protective gas, apply the voltage of 0.5-2.5V to described electrochemical cell, make to ionize from described anode
The Li gone out+It is deposited on negative electrode C, obtains described LiC6Presoma.
8. the preparation method of anode active material of lithium ion battery as claimed in claim 7, it is characterised in that
By the 40-100 DEG C of drying under vacuum of post-depositional negative electrode, by described LiC6Presoma is shelled from described negative electrode
Carry out ball milling or sand milling from getting off, obtain nano level LiC6Presoma.
9. the preparation method of the anode active material of lithium ion battery as described in claim 5 or 8, its feature exists
In, described LiC6The particle diameter of presoma is 10-80nm.
10. a lithium ion battery, it is characterised in that described lithium ion battery comprises such as claim 1-4
According to any one of anode active material of lithium ion battery.
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| CN107665983A (en) * | 2017-08-07 | 2018-02-06 | 深圳市德方纳米科技股份有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5601796A (en) * | 1995-11-22 | 1997-02-11 | The Board Of Regents Of The University Of Oklahoma | Method of making spinel LI2MN204 compound |
| CN101036251A (en) * | 2004-09-28 | 2007-09-12 | 塔迪兰电池有限公司 | Improved lithium cell and method of forming same |
| CN101950801A (en) * | 2010-09-21 | 2011-01-19 | 新疆金盛科达有色金属新材料有限责任公司 | Preparation method of positive electrode material LiFePO4/C of lithium ion battery |
| CN103078105A (en) * | 2013-01-23 | 2013-05-01 | 宁德新能源科技有限公司 | Lithium ion battery, positive active material thereof and preparation method of positive active material |
| CN103107309A (en) * | 2013-01-31 | 2013-05-15 | 中国科学技术大学 | Lithium ion battery positive pole and preparation method thereof |
-
2016
- 2016-04-27 CN CN201610268679.1A patent/CN105845909B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5601796A (en) * | 1995-11-22 | 1997-02-11 | The Board Of Regents Of The University Of Oklahoma | Method of making spinel LI2MN204 compound |
| CN101036251A (en) * | 2004-09-28 | 2007-09-12 | 塔迪兰电池有限公司 | Improved lithium cell and method of forming same |
| CN101950801A (en) * | 2010-09-21 | 2011-01-19 | 新疆金盛科达有色金属新材料有限责任公司 | Preparation method of positive electrode material LiFePO4/C of lithium ion battery |
| CN103078105A (en) * | 2013-01-23 | 2013-05-01 | 宁德新能源科技有限公司 | Lithium ion battery, positive active material thereof and preparation method of positive active material |
| CN103107309A (en) * | 2013-01-31 | 2013-05-15 | 中国科学技术大学 | Lithium ion battery positive pole and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107665983A (en) * | 2017-08-07 | 2018-02-06 | 深圳市德方纳米科技股份有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery |
| CN107665983B (en) * | 2017-08-07 | 2021-01-12 | 深圳市德方纳米科技股份有限公司 | Lithium ion battery positive electrode material, preparation method thereof and lithium ion battery |
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