CN107369815A - A kind of lithium rechargeable battery composite positive pole and preparation method thereof - Google Patents
A kind of lithium rechargeable battery composite positive pole and preparation method thereof Download PDFInfo
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- CN107369815A CN107369815A CN201710384214.7A CN201710384214A CN107369815A CN 107369815 A CN107369815 A CN 107369815A CN 201710384214 A CN201710384214 A CN 201710384214A CN 107369815 A CN107369815 A CN 107369815A
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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
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
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- 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 discloses a kind of lithium rechargeable battery composite positive pole and preparation method thereof, the material includes the cobalt acid lithium of nickelic positive electrode and poor lithium state, by using poor lithium state cobalt acid lithium as means, the residual lithium in high-nickel material top layer can effectively be removed and to high-nickel material surface structure without destruction, so as to increase the surface structure stability of material and storage performance, be advantageous to the performance of cycle performance, simultaneously, the present invention generates the poor lithium state cobalt acid lithium with electro-chemical activity while the residual lithium in effectively elimination high-nickel material top layer, effectively increase the high rate performance and coulombic efficiency of material, so as to further improve the charging and discharging capacity of material.
Description
Technical field
The invention belongs to cell art, and in particular to a kind of lithium rechargeable battery composite positive pole and its preparation
Method.
Background technology
Lithium ion battery is as a kind of chargeable secondary cell, and because its energy density is high, self discharge is small, cycle life
The advantage such as long has been widely used in the digital electronic goods such as notebook, mobile phone.In particular with carrying out the continuous of oil price this year
Go up and the getting worse of environmental pollution, the development of pure electric automobile increasingly causes the concern in terms of government and enterprise.
A key factor of limitation Development of Electric Vehicles is exactly the life that its course continuation mileage is not met by people at present
Demand.Therefore, high-energy-density is developed, the anode material for lithium-ion batteries of long circulation life also just becomes more and more urgent.Its
In the material such as positive electrode particularly NCA and NCM811 of nickelic system cause extensive concern and the research of people.
Although the high-nickel materials such as nickel cobalt lithium aluminate are with higher charging and discharging capacity, with material system, nickel contains
The rise of amount, the caused chemical property of surface-active and top layer the residual alkali such as lithium hydroxide, carbonic acid lithium content of material decline
It is also increasingly severe to subtract problem.Existing ameliorative way be usually to positive pole material surface carry out metal oxide, fluoride or
The phosphatic cladding of person.But the residual lithium of skim-coat can not effectively be gone by the method for cladding, increase covering amount can cause material again
The reduction of discharge capacity.
Or by being washed to high-nickel material, the method for the residual alkali wash-off on top layer is lifted the storage of material and followed
Ring performance.But the method for washing would generally destroy the surface structure of material, so as to cause material coulombic efficiency, charge/discharge capacity etc.
Reduction, it is impossible to meet electrical property demand.
In addition, also will by the way that high-nickel material and other commercial electrode materials are mixed or compound method, to
Hope the shortcomings that existing by other electrode materials come a certain degree of counteracting or reduction high-nickel material.Such as application number
201410461935.X patent of invention " a kind of anode material for lithium-ion batteries of high power capacity and preparation method thereof " is described, by nickel
Two kinds of active materials of cobalt lithium aluminate and cobalt acid lithium are well mixed according to a certain percentage, are added in trivalent silicon source solution and are stirred formation
Solidliquid mixture, silicon source solution is evenly coated at active material particle surface, then be dried and formed through calcining.It is but above-mentioned
The method of this compound coating is still by can not effectively remove nickelic system skin-material or deficiency mentioned above still be present, no
It can effectively improve high-nickel material built-in problem.
The content of the invention
The problem of existing for prior art, it is an object of the invention to provide a kind of lithium rechargeable battery anode composite
Material, the material include the cobalt acid lithium of nickelic positive electrode and poor lithium state, significantly reduce the residual lithium in top layer of nickelic system material,
Effectively improve specific capacity, coulombic efficiency and cycle life of material etc..
It is a further object of the present invention to provide a kind of preparation method of lithium rechargeable battery composite positive pole.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of lithium rechargeable battery composite positive pole, including the nickelic positive electrode of lithium rechargeable battery and poor lithium state
Cobalt acid lithium, the nickelic positive electrode of lithium rechargeable battery is with formula Li1+xNi1-y-zCoyMzO2What is represented is compound containing lithium
Oxide, M are Mn at least one element selected from Al, 0<X≤0.2,0≤y≤0.4,0≤z≤0.4,0≤y+z≤0.6, institute
The cobalt acid lithium for stating poor lithium state is with formula LiaCoO2The lithium-contained composite oxide of expression, 0 ＜ a ＜ 1.
Further, the cobalt acid lithium of poor lithium state weight shared in the lithium rechargeable battery composite positive pole
It is 0.1~40%, preferably 0.1~33% to measure fraction.
Further, the median particle diameter of the nickelic positive electrode of the lithium rechargeable battery is 2-20 μm, preferably 7~12 μ
m。
Further, the median particle diameter of the cobalt acid lithium of the poor lithium state is 0.1~15 μm, preferably 0.6~2 μm.
Further, the crystal structure of the cobalt acid lithium of the poor lithium state can be stratiform, spinelle or rock salt structure.
The preparation method of above-mentioned lithium rechargeable battery composite positive pole comprises the following steps：
1) by Ni1-y-zCoyMz(OH)2It is sintered, is cooled to after room temperature i.e. after being mixed with lithium source according to mol ratio 1-1.2
Obtain Li1+xNi1-y-zCoyMzO2Lithium-containing oxides；
2) Li for obtaining cobalt source and step 1)1+xNi1-y-zCoyMzO2Lithium-containing oxides is mixed according to mol ratio 0.001-0.5
It is sintered after conjunction, that is, obtains the lithium ion secondary of the cobalt acid lithium comprising the nickelic positive electrode of lithium rechargeable battery and poor lithium state
Battery composite anode material.
Further, in step 1), the lithium source is selected from lithium hydroxide, lithium carbonate, and one in lithium acetate or lithium nitrate
Kind is a variety of.
Further, the temperature range being sintered in step 1) is 650-1100 DEG C, preferably 650-850 DEG C.
Further, in step 2), the cobalt source is selected from cobalt hydroxide, cobalt oxide, cobalt nitrate, cobalt acetate or LiaCoO2
One or more in (0 ＜ a ＜ 1).
Further, the Li for obtaining cobalt source and step 1) is also included in step 2)1+xNi1-y-zCoyMzO2Lithium-containing oxides
During mixing, while part lithium source is added, wherein the lithium source and the mol ratio of cobalt source that add are 0.001-1.
Further, the temperature range being sintered in step 2) is 650-1100 DEG C, preferably 650-950 DEG C.
In addition, under the central idea of the present invention, can also be realized by any means known to above-mentioned high-nickel material and poor lithium
The cladding of the lithium rechargeable battery composite positive pole of the cobalt acid lithium of state or doping.Covering material can be aluminum oxide, oxygen
Change one or more combinations of titanium, zirconium oxide, magnesia, zinc oxide and its lithium-containing oxides, li-contained phosphate.Doped chemical can
Combined with the one or more for being the elements such as magnesium, aluminium, titanium, zirconium, manganese, nickel, niobium.
The advantages of lithium rechargeable battery composite positive pole of the present invention, is as follows：
(1) present invention is by using poor lithium state cobalt acid lithium as means, can effectively remove the residual lithium in high-nickel material top layer such as lithium carbonate
With lithium hydroxide and to high-nickel material surface structure without destruction, so as to increase the surface structure stability of material and storage
Can, be advantageous to the performance of cycle performance.
(2) present invention generates while the residual lithium in effectively elimination high-nickel material top layer compares cobalt relative to standard stoichiometry
Sour lithium has been completed the transformation of semiconductor conductor 801 so as to have the poor lithium state cobalt acid lithium of high electronic conductance and ionic conductance, from
And effectively increase the high rate performance and coulombic efficiency of material.
(3) the poor lithium state with electro-chemical activity is generated while the residual lithium in high-nickel material top layer is effectively eliminated in the present invention
Cobalt acid lithium, so as to further improve the charging and discharging capacity of material.
Brief description of the drawings
Fig. 1 is the SEM image of sample after being improved in embodiment 1.
Fig. 2 is the SEM image of sample before being improved in embodiment 1.
Fig. 3 is first all charging and discharging curves of sample before and after being improved in embodiment 1.
Fig. 4 is 100 weeks cycle performance curves of sample before and after being improved in embodiment 1.
Embodiment
With reference to embodiments, the present invention is expanded on further.But these embodiments be only limitted to explanation the present invention rather than
Limit the scope of application of the present invention.
Embodiment 1
One) Li is prepared1.1Ni0.8Co0.1Mn0.1O2Lithium-containing oxides
By a hydronium(ion) lithia and 20g Ni0.8Co0.1Mn0.1(OH)2Mixed according to mol ratio 1.1.After mixing
Raw material in oxygen atmosphere according to 5 DEG C/min of heating rate by room temperature to 850 DEG C calcining 10h, naturally cool to room temperature,
Obtain Li1.1Ni0.6Co0.2Mn0.2O2Lithium-containing oxides, the product is sample before improving, as shown in Fig. 2 spheric granules in figure
As its pattern, about 10 μm of its median particle diameter.
Two) Li is prepared0.7CoO2Lithium-containing oxides
By lithium carbonate and 10g Co3O4Mixed according to lithium/cobalt mol ratio 0.7.By mixed powder in atmosphere
After 950 DEG C of calcining 5h, Li is obtained0.7CoO2Lithium-containing oxides, about 2 μm of its median particle diameter.
Three) Li is prepared1.1Ni0.8Co0.1Mn0.1O2And Li0.7CoO2Composite positive pole
By 1mol Li1.1Ni0.8Co0.1Mn0.1O2The Li of lithium-containing oxides and 0.5mol0.7CoO2Lithium-containing oxides mixes.
Mixed powder after 800 DEG C of calcining 3h, is obtained into Li in oxygen1.1Ni0.8Co0.1Mn0.1O2And Li0.7CoO2Anode composite
Material, wherein the mass fraction of poor lithium state cobalt acid lithium in the composite is about 33%.As shown in figure 1, spheric granules is in figure
For the nickle cobalt lithium manganate pattern after improvement, the little particle on surface is the pattern of poor lithium state cobalt acid lithium present in material.
Using 1-METHYLPYRROLIDONE as solvent, by gained powder after sintering with conductive black and Kynoar according to weight
Than 90:5:5 stir after be coated on clean aluminium foil surface, scratch film forming.Electrode slice is punched into diameter after forced air drying
8mm disk, further 120 DEG C of drying 6h remove moisture in vacuum drying oven.Using the electrode slice made as half-cell
Working electrode, lithium metal are to electrode, with 1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and
DMC weight is than 1:1) electrolyte is used as, battery is assembled into glove box and charge-discharge test, voltage model are carried out to its battery
It is 0.1C to enclose for 2.8-4.5V, charging and discharging currents density.First all charging and discharging curves of sample are as shown in Figure 3, it is seen that sample after improvement
The charge and discharge electric polarization of product reduces, discharge capacity lifting, and coulombic efficiency improves first.Cycle performance is as shown in Figure 4, it is seen that after improvement
The cycle performance of sample is also obviously improved.
The embodiment 1 of table 1 improves the front and rear residual lithium in sample top layer
| LiOH% | Li2CO3 | |
| Before improvement | 1.146 | 0.086 |
| After improvement | 0.057 | 0.052 |
As seen from the above table, after improvement sample top layer residual lithium, the content of particularly lithium hydroxide substantially reduces.
Embodiment 2
One) Li is prepared1.1Ni0.8Co0.1Mn0.1O2Lithium-containing oxides
By a hydronium(ion) lithia and 20g Ni0.8Co0.1Mn0.1(OH)2Mixed according to mol ratio 1.1.After mixing
Raw material in oxygen according to 5 DEG C/min of heating rate by room temperature to 900 DEG C calcining 10h, naturally cool to room temperature, obtain
Li1.1Ni0.6Co0.2Mn0.2O2Lithium-containing oxides, about 12 μm of its median particle diameter.
Two) Li is prepared1.1Ni0.8Co0.1Mn0.1O2And Li0.83CoO2Composite positive pole
By 1mol Li1.1Ni0.8Co0.1Mn0.1O2Lithium-containing oxides and 0.12mol cobalt acetate dissolve in ethanol, stir
Mix and dried after being evaporated in 120 DEG C of baking ovens.Powder after drying after 800 DEG C of calcining 3h, is obtained in oxygen
Li1.1Ni0.8Co0.1Mn0.1O2And Li0.83CoO2Composite positive pole, about 11 μm of the median particle diameter of obtained composite, wherein
The mass fraction of poor lithium state cobalt acid lithium in the composite is about 11%.
Using 1-METHYLPYRROLIDONE as solvent, by gained powder after sintering with conductive black and Kynoar according to weight
Than 90:5:5 stir after be coated on clean aluminium foil surface, scratch film forming.Electrode slice is punched into diameter after forced air drying
8mm disk, further 120 DEG C of drying 6h remove moisture in vacuum drying oven.Using the electrode slice made as half-cell
Working electrode, lithium metal are to electrode, with 1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and
DMC weight is than 1:1) electrolyte is used as, battery is assembled into glove box and charge-discharge test, voltage model are carried out to its battery
It is 0.1C to enclose for 2.8-4.5V, charging and discharging currents density.
Embodiment 3
Embodiment 2 is copied, 0.05mol aluminum nitrates are simply added while cobalt acetate is added to realize to above-mentioned positive pole material
The aluminium cladding of material.The median particle diameter of wherein poor lithium state cobalt acid lithium is about 0.8 μm, and its mass fraction in the composite is about
11%.Working electrode using the electrode slice made as half-cell, lithium metal are to electrode, with 1mol/L LiPF6/ ethene
Carbonic ester (EC)-dimethyl carbonate (DMC) (EC and DMC weight ratio 1:1) electrolyte is used as, electricity is assembled into glove box
Pond simultaneously carries out charge-discharge test to its battery, and voltage range 2.8-4.5V, charging and discharging currents density is 0.1C.
Embodiment 4-6
Embodiment 2 is copied, cobalt acetate therein is simply changed to the cobalt oxide, cobalt hydroxide, cobalt nitrate of suitable mole,
The median particle diameter of the cobalt acid lithium of obtained poor lithium state respectively may be about 4 μm, 2 μm, 0.6 μm, and poor lithium state cobalt acid lithium is in the composite
Mass fraction be about 11%.Working electrode using the electrode slice made as half-cell, lithium metal are to electrode, are used
1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and DMC weight ratio 1:1) electrolyte is used as,
Battery is assembled into glove box and charge-discharge test is carried out to its battery, voltage range 2.8-4.5V, charging and discharging currents are close
Spend for 0.1C.
Embodiment 7-10
Embodiment 1 is copied, simply by Li therein1.1Ni0.8Co0.1Mn0.1O2Replace with successively
Li1.1Ni0.8Co0.1Al0.1O2、Li1.1Ni0.815Co0.15Al0.035O2、Li1.05Ni0.6Co0.2Mn0.2O2With
Li1.2Ni0.6Co0.2Mn0.2O2, the mass fraction of poor lithium state cobalt acid lithium in the composite is about 33%.The electrode that will be made
Working electrode of the piece as half-cell, lithium metal are to electrode, with 1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbon
Acid esters (DMC) (EC and DMC weight ratio 1:1) electrolyte is used as, battery is assembled into glove box and its battery is filled
Discharge test, voltage range 2.8-4.5V, charging and discharging currents density are 0.1C.
Embodiment 11-12
Embodiment 3 is copied, aluminum nitrate therein is simply changed to aluminium isopropoxide, butyl titanate successively, by what is made
Working electrode of the electrode slice as half-cell, lithium metal are to electrode, with 1mol/L LiPF6/ vinyl carbonate (EC)-diformazan
Base carbonic ester (DMC) (EC and DMC weight ratio 1:1) electrolyte is used as, battery is assembled into glove box and its battery is entered
Row charge-discharge test, voltage range 2.8-4.5V, charging and discharging currents density are 0.1C.
Embodiment 13
Embodiment 2 is copied, 0.03mol lithium hydroxide, obtained poor lithium state are simply added while cobalt acetate is added
The median particle diameter of cobalt acid lithium be about 1.1 μm.Working electrode using the electrode slice made as half-cell, lithium metal are to electricity
Pole, with 1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and DMC weight ratio 1:1) as electricity
Liquid is solved, battery is assembled into glove box and charge-discharge test, voltage range 2.8-4.5V, discharge and recharge electricity are carried out to its battery
Current density is 0.1C.
Embodiment 14
Embodiment 1 is copied, simply by step 1) in sintering temperature be adjusted to 850 DEG C, the intermediate value of obtained nickelic product
Particle diameter is about 9 μm, the working electrode using the electrode slice made as half-cell, and lithium metal is to electrode, uses 1mol/L
LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and DMC weight ratio 1:1) electrolyte is used as, in glove box
In be assembled into battery and to its battery carry out charge-discharge test, voltage range 2.8-4.5V, charging and discharging currents density is 0.1C.
Embodiment 15
Embodiment 2 is copied, simply by step 2) in sintering temperature be adjusted to 650 DEG C, the cobalt acid lithium of obtained poor lithium state
Median particle diameter be about 1.2 μm.Working electrode using the electrode slice made as half-cell, lithium metal are to electrode, are used
1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and DMC weight ratio 1:1) electrolyte is used as,
Battery is assembled into glove box and charge-discharge test is carried out to its battery, voltage range 2.8-4.5V, charging and discharging currents are close
Spend for 0.1C.
Embodiment 16-18
Embodiment 1 is copied, simply by Li therein1.1Ni0.8Co0.1Mn0.1O2Replace with successively：Li1.1Ni0.8Co0.2O2、
Li1.1Ni0.8Mn0.2O2And Li1.1Ni0.7Mn0.2Al0.1O2, the median particle diameter of the high-nickel material respectively may be about 8 μm, 7.5 μm and 7 μ
m.Working electrode using the electrode slice made as half-cell, lithium metal are to electrode, with 1mol/L LiPF6/ ethene carbonic acid
Ester (EC)-dimethyl carbonate (DMC) (EC and DMC weight ratio 1:1) electrolyte is used as, battery is assembled into glove box simultaneously
Charge-discharge test is carried out to its battery, voltage range 2.8-4.5V, charging and discharging currents density is 0.1C.
Embodiment 19
Embodiment 1 is copied, simply by Ni therein0.8Co0.1Mn0.1(OH)2Replace with Ni (OH)2, the high-nickel material
Median particle diameter is about 8 μm.Working electrode using the electrode slice made as half-cell, lithium metal are to electrode, use 1mol/L
LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and DMC weight ratio 1:1) electrolyte is used as, in glove box
In be assembled into battery and to its battery carry out charge-discharge test, voltage range 2.8-4.5V, charging and discharging currents density is 0.1C.
Embodiment 20
Embodiment 1 is copied, simply by 0.5mol therein Li0.7CoO2Lithium-containing oxides replaces with 0.001mol's
Li0.7CoO2Lithium-containing oxides, the median particle diameter of the high-nickel material is about 8 μm, wherein poor lithium state cobalt acid lithium is in the composite
Mass fraction be about 0.1%.Working electrode using the electrode slice made as half-cell, lithium metal are to electrode, are used
1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and DMC weight ratio 1:1) electrolyte is used as,
Battery is assembled into glove box and charge-discharge test is carried out to its battery, voltage range 2.8-4.5V, charging and discharging currents are close
Spend for 0.1C.
The electrochemistry circulation of above-described embodiment the results are shown in Table 2：
Table 2 (charging and discharging capacity=charge/discharge capacity/combination electrode material quality)
As seen from the above table, the material after being improved according to the technical scheme in the present invention can effectively remove material table
The lithium hydroxide and lithium carbonate of face electronic isolation generate the poor lithium state cobalt acid lithium with electro-chemical activity simultaneously, and further
The surface texture stability and charge transfer characteristic of material are modified and improve, so as to play and circulate with relatively good capacity
Stability.
Claims (10)
1. a kind of lithium rechargeable battery composite positive pole, including the nickelic positive electrode of lithium rechargeable battery and poor lithium state
Cobalt acid lithium, the nickelic positive electrode of lithium rechargeable battery is with formula Li1+xNi1-y-zCoyMzO2The composite oxygen containing lithium represented
Compound, M are Mn at least one element selected from Al, 0<X≤0.2,0≤y≤0.4,0≤z≤0.4,0≤y+z≤0.6 are described
The cobalt acid lithium of poor lithium state is with formula LiaCoO2The lithium-contained composite oxide of expression, 0 ＜ a ＜ 1.
2. a kind of lithium rechargeable battery composite positive pole as claimed in claim 1, it is characterised in that the poor lithium state
Cobalt acid lithium weight fraction shared in the lithium rechargeable battery composite positive pole is 0.1~40%.
A kind of 3. lithium rechargeable battery composite positive pole as claimed in claim 1, it is characterised in that the lithium ion two
The median particle diameter of the nickelic positive electrode of primary cell is 2-20 μm.
4. a kind of lithium rechargeable battery composite positive pole as claimed in claim 1, it is characterised in that the poor lithium state
The median particle diameter of cobalt acid lithium is 0.1~15 μm.
5. a kind of lithium rechargeable battery composite positive pole as claimed in claim 1, it is characterised in that the poor lithium state
The crystal structure of cobalt acid lithium is stratiform, spinelle or rock salt structure.
6. the preparation method of the lithium rechargeable battery composite positive pole described in claim any one of 1-5, including following step
Suddenly：
1) by Ni1-y-zCoyMz(OH)2It is sintered after being mixed with lithium source according to mol ratio 1-1.2, is obtained after being cooled to room temperature
Li1+xNi1-y-zCoyMzO2Lithium-containing oxides；
2) Li for obtaining cobalt source and step 1)1+xNi1-y-zCoyMzO2After lithium-containing oxides mixes according to mol ratio 0.001-0.5
It is sintered, the lithium rechargeable battery for obtaining the cobalt acid lithium comprising the nickelic positive electrode of lithium rechargeable battery and poor lithium state is answered
Close positive electrode.
7. preparation method as claimed in claim 6, it is characterised in that in step 1), the lithium source is selected from lithium hydroxide, carbonic acid
One or more in lithium, lithium acetate or lithium nitrate.
8. preparation method as claimed in claim 6, it is characterised in that step 1) and 2) in the temperature range that is sintered be
650-1100℃。
9. preparation method as claimed in claim 6, it is characterised in that in step 2), the cobalt source is selected from cobalt hydroxide, oxidation
Cobalt, cobalt nitrate, cobalt acetate or LiaCoO2In one or more.
10. preparation method as claimed in claim 6, it is characterised in that also include obtaining cobalt source and step 1) in step 2)
Li1+xNi1-y-zCoyMzO2Part lithium source is added while lithium-containing oxides mixes, the mol ratio of the lithium source and cobalt source is
0.001-1。
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| CN108550833A (en) * | 2018-05-18 | 2018-09-18 | 宁德新能源科技有限公司 | A kind of positive electrode and lithium ion battery |
| CN108550830A (en) * | 2018-05-11 | 2018-09-18 | 哈尔滨工业大学深圳研究生院 | Anode material for lithium-ion batteries and preparation method thereof |
| CN108695502A (en) * | 2018-05-22 | 2018-10-23 | 青海泰丰先行锂能科技有限公司 | A kind of lithium ion battery composite cathode material and preparation method thereof |
| CN112424125A (en) * | 2018-06-28 | 2021-02-26 | 巴斯夫欧洲公司 | Method for processing nickel-rich electrode active material |
| CN113471414A (en) * | 2020-03-31 | 2021-10-01 | 北京卫蓝新能源科技有限公司 | Lithium ion battery composite positive electrode material and preparation method and application thereof |
| WO2021248272A1 (en) * | 2020-06-08 | 2021-12-16 | 宁德新能源科技有限公司 | Positive electrode material and electrochemical device containing same |
| CN115676910A (en) * | 2021-07-21 | 2023-02-03 | 天津国安盟固利新材料科技股份有限公司 | Preparation method of lithium-rich manganese-based positive electrode material |
| WO2023241195A1 (en) * | 2022-06-17 | 2023-12-21 | 宁德新能源科技有限公司 | Positive electrode material, electrochemical apparatus comprising same, and electronic apparatus |
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| CN108550830A (en) * | 2018-05-11 | 2018-09-18 | 哈尔滨工业大学深圳研究生院 | Anode material for lithium-ion batteries and preparation method thereof |
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| CN108695502A (en) * | 2018-05-22 | 2018-10-23 | 青海泰丰先行锂能科技有限公司 | A kind of lithium ion battery composite cathode material and preparation method thereof |
| CN112424125A (en) * | 2018-06-28 | 2021-02-26 | 巴斯夫欧洲公司 | Method for processing nickel-rich electrode active material |
| CN112424125B (en) * | 2018-06-28 | 2024-03-15 | 巴斯夫欧洲公司 | Method for processing nickel-rich electrode active material |
| CN113471414A (en) * | 2020-03-31 | 2021-10-01 | 北京卫蓝新能源科技有限公司 | Lithium ion battery composite positive electrode material and preparation method and application thereof |
| WO2021248272A1 (en) * | 2020-06-08 | 2021-12-16 | 宁德新能源科技有限公司 | Positive electrode material and electrochemical device containing same |
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| CN115676910A (en) * | 2021-07-21 | 2023-02-03 | 天津国安盟固利新材料科技股份有限公司 | Preparation method of lithium-rich manganese-based positive electrode material |
| CN115676910B (en) * | 2021-07-21 | 2024-04-19 | 天津国安盟固利新材料科技股份有限公司 | Preparation method of lithium-rich manganese-based positive electrode material |
| WO2023241195A1 (en) * | 2022-06-17 | 2023-12-21 | 宁德新能源科技有限公司 | Positive electrode material, electrochemical apparatus comprising same, and electronic apparatus |
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