CN109326794A - A kind of anode material of lithium battery and preparation method thereof and lithium battery - Google Patents
A kind of anode material of lithium battery and preparation method thereof and lithium battery Download PDFInfo
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- CN109326794A CN109326794A CN201811207152.3A CN201811207152A CN109326794A CN 109326794 A CN109326794 A CN 109326794A CN 201811207152 A CN201811207152 A CN 201811207152A CN 109326794 A CN109326794 A CN 109326794A
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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
- 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
- H01M4/52—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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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 anode material of lithium battery and preparation method thereof and lithium batteries.The anode material of lithium battery is that richness lithium Gao Meng mixes tungsten positive electrode, chemical formula Li1+δNiaCobMncWeO2, wherein δ=0~0.2, a=0.05~0.35, b=0.05~0.3, c=0.45~0.7, e=0.005~0.012, which has high-energy density in battery charge and discharge process, and has high discharge capacity.The presoma of the anode material of lithium battery is prepared by coprecipitation reaction by the present invention, then the presoma and lithium compound is mixed, calcining, obtains the anode material of lithium battery.Lithium battery pack of the invention contains the anode material of lithium battery, has good cycle performance and high magnification based on the richness lithium Gao Meng lithium battery for mixing tungsten positive electrode.
Description
Technical field
The present invention relates to technical field of lithium batteries, and in particular to a kind of anode material of lithium battery and preparation method thereof and one kind
Lithium battery.
Background technique
Global energy crisis and the environmental pollution got worse, make it necessary to develop the novel friendship based on clean energy resource
Logical tool.And the power resources as new traffic tool, new type lithium ion battery belong to clean energy resource, have safety good,
The advantages that cyclicity is good, and the service life is long, nontoxic and pollution-free.
Lithium ion battery generally includes anode, cathode, partition and electrolyte.The lithium ion battery in the present age is generally negative with carbon
Pole (or anode) and transition metal oxide are positive (or cathode).Cathode and anode are usually layer structure to accommodate lithium ion,
During charging and discharging, lithium ion transmits between a cathode and an anode.
Important component of the positive electrode as lithium ion battery is the key factor for determining cell safety, capacity and price.
In the current lithium ion battery commercially produced, the cost of positive electrode accounts about the 20~40% of entire battery cost,
The reduction of positive electrode price directly decides the reduction of lithium ion battery price, especially true to lithium-ion-power cell.Separately
Outside, motive-power battery heavy-current discharge, specific energy, safety and in terms of particular/special requirement, more highlight anode
The importance of material.And all there are no be fully achieved for the current anode material for lithium-ion batteries for studying and being try to application
It is required that greatly constraining the development of lithium-ion-power cell.
The anode of first generation lithium ion battery is cobalt acid lithium (LiCoO2), this is a kind of lamellar compound, and oxygen atom is with close
Stacked form is constituted, and this structure is formed and the comparable octahedral interstices of oxygen atom quantity.In cobalt acid lithium, one layer of cobalt and one layer
Lithium alternately inserts these octahedral interstices.(voltage is higher than 4.3V), lamellar compound meeting when half lithium is removed from cobalt acid lithium
Become unstable.Expensive due to cobalt metal, the price of cobalt acid lithium is also higher.In order to improve its performance and reduce cost,
Nickel and manganese atom are used to replace cobalt, and obtained product still maintains laminated structure.These general compounds are referred to as three
First material (NCM).
Initial ternary material is LiNi0.333Co0.333Mn0.333O2.In order to increase capacitance, ternary material structure and at
The improvement divided divides both direction, first is that improving nickel content, such as LiNi0.5Co0.3Mn0.2, another is improve lithium and manganese opposite
Content, the high manganese material of rich lithium such as proposed at Argonne National Laboratory (Argonne Nantional Lab).The rich high manganese material of lithium
Due to lithium excess, the mixture of two kinds of structures is formed in nanometer level.This material has general expression X LiM ' O2-(1-x)
Li2MnO3, wherein 0 < X < 1, and wherein M is one or more ions, average trivalent oxidation state and there is at least one ion to deposit
Mn or Ni, and wherein M ' is one or more ions, average tetravalence oxidation state.
The performance of the rich high manganese material of lithium is related with its ingredient, especially and Li2MnO3Content it is related.High Li2MnO3Content
Material with its high reversible capacity, once posted with the great expectations of the following height ratio capacity cell positive material, but its commercialization always
It is not able to achieve slowly, one of main problem is multiplying power.Therefore there is an urgent need to provide a kind of low price effectively high manganese material of rich lithium
Material, but the rich lithium technology of high Mn content is difficult to realize, the excessively high multiplying power that will will affect lithium battery of manganese content of the rich high manganese material of lithium.
Meanwhile the specific volume metric density and high rate performance of positive electrode can be improved in witch culture appropriate, Gao Meng, which mixes tungsten, can be realized rich lithium
The high magnification of high manganese material, but the high manganese material of rich lithium of Doped Tungsten does not have been reported that yet under the conditions of Gao Meng.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of anode material of lithium battery.The anode material
Material has high-energy density in battery charge and discharge process, and has high discharge capacity.
The object of the invention is also to provide the methods for preparing a kind of above-mentioned anode material of lithium battery.
Another object of the present invention is to provide a kind of lithium batteries comprising above-mentioned anode material of lithium battery.It should be based on upper
Stating the lithium battery that rich lithium Gao Meng mixes tungsten positive electrode has good cycle performance and high magnification.
The purpose of the present invention is achieved through the following technical solutions.
A kind of anode material of lithium battery mixes tungsten positive electrode, chemical formula Li for richness lithium Gao Meng1+δNiaCobMncWeO2,
In, δ=0~0.2, a=0.05~0.35, b=0.05~0.3, c=0.45~0.7, e=0.005~0.012.
Preferably, a kind of anode material of lithium battery, chemical formula Li1+δNiaCobMncWeO2, wherein δ=0~0.2, a=
0.05~0.35, b=0.05~0.3, c=0.45~0.7, e=0.005~0.010.
Preferably, the xLiMO of two-phase is formed in the anode material of lithium battery2·(1-x)Li2MnO3, i.e. LiMO2With
Li2MnO3The mixture in nano-level, wherein 0 < x < 1, M be higher than 3+ valence the metallic element including Ni, Co and Mn
Combination.
Preferably, the anode material of lithium battery carries out charge and discharge under conditions of 25 DEG C, 2.0~4.6V, 1/10C,
Discharge capacity is greater than 205mAh/g.
Preferably, the anode material of lithium battery carries out charge and discharge, 2C electric discharge under conditions of 25 DEG C, 2.0~4.6V
Capacity is 96% or more of 0.2C discharge capacity.
The method for preparing anode material of lithium battery described in any of the above embodiments, includes the following steps:
(1) soluble-salt of tungsten is soluble in water with precipitating reagent and be uniformly mixed, obtain precipitant mix solution；
(2) the soluble-salt mixed solution of precipitant mix solution and nickel, cobalt and manganese is added to the water and be co-precipitated instead
It answers, obtains presoma；
(3) obtained presoma and lithium compound are mixed, calcining, obtains the anode material of lithium battery.
Preferably, in step (1), the soluble-salt of the tungsten includes one in the sulfate of tungsten, nitrate and acetate
Kind or more.
Preferably, in step (1), the precipitating reagent includes one or more of sodium carbonate and sodium hydroxide.
Preferably, in step (1), the concentration of the precipitant mix solution is 1.0~2.0mol/L.
Preferably, in step (2), the concentration of the soluble-salt mixed solution of the nickel, cobalt and manganese is 1.0~2.0mol/
L, solvent are deionized water.
Preferably, in step (2), in the soluble-salt mixed solution of the nickel, brill and manganese, the molar ratio of nickel, brill and manganese
It is 0.05~0.4: 0.05~0.3: 0.5~0.8.
Preferably, in step (2), the soluble-salt of the nickel, cobalt and manganese includes the sulfate and manganese of the sulfate of nickel, cobalt
Sulfate.
Preferably, in step (2), the precipitant mix solution is total with the soluble-salt mixed solution of nickel, cobalt and manganese
In mixed solution, the molar ratio of precipitating reagent and tungsten, nickel, cobalt and the total metal of manganese is 1: 1.
Preferably, in step (2), the soluble-salt mixed solution of the precipitant mix solution and nickel, cobalt and manganese is added
Flow velocity in water is 3~7ml/min.
Preferably, in step (2), the temperature of the coprecipitation reaction is 50~60 DEG C, and the time is 8~12 hours.
Preferably, in step (2), the general formula of the presoma is NiqCorMnsWtCO3, wherein 0.05 < q < 0.4,
0.05 < r <, 0.3,0.5 < s <, 0.7,0 < t < 0.05.
Preferably, in step (3), the lithium compound includes one or more of lithium carbonate and lithium hydroxide.
Preferably, in step (3), the presoma and lithium compound are according to tungsten, nickel, cobalt and the total metallic element of manganese and lithium
The ratio mixing that molar ratio is 1: 1.1~1: 1.2.
Preferably, in step (3), the calcining is to keep the temperature 6~20 hours for 500~650 DEG C in calcining furnace, then at 750
~1000 DEG C keep the temperature 9~24 hours.
A kind of lithium ion battery, including negative electrode material, partition and electrolyte also include lithium battery described in any of the above embodiments
Positive electrode.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
The present invention adulterates wolfram element in the high manganese anode material of rich lithium for the first time, and obtain high Mn content mixes tungsten anode material
Material, and preparation method is easily operated, preparation cost is low, while richness lithium Gao Meng mixes tungsten positive electrode with high-energy density, tool
There is high discharge capacity, good cycle performance and more high power are had based on the richness lithium Gao Meng lithium battery for mixing tungsten positive electrode
Rate.
Detailed description of the invention
Fig. 1 is the charging and discharging curve of the half-cell of the high manganese anode material of rich lithium prepared based on embodiment 1 and embodiment 2
Figure；
Fig. 2 is the x-ray diffraction pattern of the high manganese anode material of rich lithium prepared by embodiment 2；
Fig. 3 is the charge and discharge cycles curve graph of the half-cell of the high manganese anode material of rich lithium prepared based on embodiment 2；
Fig. 4 is the half-cell for being the high manganese anode material of 0.7mol% richness lithium based on the witch culture amount prepared in embodiment 3
Charge-discharge performance curve graph；
Fig. 5 is filling based on the half-cell that the witch culture amount prepared in embodiment 4 is the high manganese anode material of 0mol% richness lithium
Discharge performance curve graph；
It is 0.7mol%, 1.5mol% richness lithium Gao Meng that Fig. 6, which is based on the witch culture amount prepared in embodiment 3 and embodiment 5,
The charge and discharge cycles curve graph of the half-cell of positive electrode.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment and attached drawing, but this hair
Bright protection scope and embodiment is without being limited thereto.Test method without specific conditions in embodiment, usually according to routine
Condition or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise all percentage, ratio, ratio or number
It is by weight.Unless otherwise defined, it anticipates known to used all professional and scientific terms and one skilled in the art
Justice is identical.
The positive electrode that embodiment is prepared measures its performance by the preparation of button cell:
The chemical property of positive electrode is embodied by coin half cell.Half-cell anode electrode is by positive material
Material: conductive agent (Super P): binder (PVDF) is made with 80: 10: 10 mass ratio.
Half-cell anode preparation procedure is as follows: positive electrode and the Super P from MTI company are mixed to form homogeneous powder
Last mixture.Polyvinylidene fluoride PVDF (MTI company) is dissolved with NMP (N-Methyl pyrrolidone) (MTI company), stirred
Night, to form PVDF-NMP solution.The mixture of powders of positive electrode and SuperP is added in PVDF-NMP solution and is mixed
4 hours are closed to form slurry.The slurry is applied to aluminium foil collector (MTI company) to form thin wet film.The anode of coating
Electrode under vacuum 120 DEG C drying 6 hours to remove NMP.It is then transferred into the glove box of argon gas filling.
The preparation of nummular lithium battery: using the anode of preparation as lithium battery anode, lithium chip (MTI company) is used as negative electricity
Pole.Electrolyte solution be 1M LiPF6 is dissolved in ethylene carbonate diethyl carbonate and dimethyl carbonate with volume ratio 1: 1: 1
Composition mixture (MTI company).Diaphragm is three-layer polypropylene film (Celgard company).
Embodiment 1
Lithium-rich anode material Li without witch culture1.1Ni0.22Co0.22Mn0.47O2Preparation, the specific steps are as follows:
(1) persursor material (Ni0.24Co0.24Mn0.52)2CO3Preparation, by each element group in the chemical formula of persursor material
The stoichiometric ratio divided, by 12.6g NiSO4·6H2O、13.5g CoSO4·7H2O and 17.5g MnSO4·H2O is dissolved in
In 100ml deionized water, the sulfuric acid mixed salt solution that concentration is 2.0mol/L is obtained；
(2) precipitant solution with sulfuric acid mixed salt solution same volume is prepared, concentration is the Na of 2.0mol/L2CO3It is molten
Liquid；
(3) 50ml deionized water is added in 500ml beaker, temperature is maintained 55 DEG C, persistently stirred using electric mixer
It mixes, then 10mL sulfuric acid mixed salt solution and 10mL precipitant solution is added in deionized water together with the flow velocity of 5ml/min,
60 DEG C progress coprecipitation reaction 8 hours；After reaction, obtained co-precipitate is obtained after washing, filtering, drying
Presoma, chemical formula are (Ni0.24Co0.24Mn0.52)2CO3；
(4) ratio for being 1: 1.2 according to the molar ratio of nickel, cobalt and the total metallic element of manganese and lithium, by lithium carbonate and presoma
It is uniformly mixed, in tube calciner, keeps the temperature 5 hours with 600 DEG C, be then warming up to 920 DEG C and keep the temperature 24 hours, furnace cooling
Afterwards, the high manganese anode material Li of rich lithium is obtained1.1Ni0.22Co0.22Mn0.47O2。
By the high manganese anode material Li of the rich lithium of acquisition1.1Ni0.22Co0.22Mn0.47O2It is assembled into R2032 type button half-cell,
Carry out charge-discharge test under conditions of 25 DEG C, 2.0~4.6V, 1/10C, the charge and discharge of charging and discharging curve figure sample 1 as shown in figure 1
Shown in curve, as shown in Figure 1, discharge capacity 190mAH/g.
Embodiment 2
The lithium-rich anode material Li of Doped Tungsten1.1Ni0.22Co0.22Mn0.47W0.01O2Preparation, the specific steps are as follows:
Same as Example 1, difference is: the ratio of nickel cobalt manganese change and precipitant solution in joined
1mol percentage tungsten compound Na2WO3·2H2O, presoma chemical formula are (Ni0.24Co0.24Mn0.51W0.01)2CO3, it is prepared
Witch culture amount is the high manganese anode material presoma of rich lithium of 1.0mol%.
The ratio for being 1: 1.2 according to the molar ratio of tungsten, nickel, cobalt and the total metallic element of manganese and lithium, by lithium carbonate and presoma
(Ni0.24Co0.24Mn0.51W0.01)2CO3It is uniformly mixed, in tube calciner, keeps the temperature 5 hours with 600 DEG C, be then warming up to 920
DEG C heat preservation 24 hours, after furnace cooling, obtain the rich high manganese anode material Li of lithium1.1Ni0.22Co0.22Mn0.47W0.01O2。
The x-ray diffraction pattern of the high manganese anode material of rich lithium of preparation is as shown in Fig. 2, as shown in Figure 2, being successfully prepared and mixing
The lithium-rich anode material Li of miscellaneous tungsten1.1Ni0.22Co0.22Mn0.47W0.01O2。
By the high manganese anode material Li of obtained rich lithium1.1Ni0.22Co0.22Mn0.47W0.01O2It is assembled into half electricity of R2032 type button
Pond, carry out charge-discharge test under conditions of 25 DEG C, 2.0~4.6V, 1/10C, and sample 2 fills charging and discharging curve figure as shown in figure 1
Shown in discharge curve, as shown in Figure 1, discharge capacity 205mAh/g obtains that discharge capacity is high to mix under the conditions of high additive Mn
The high manganese anode material of tungsten richness lithium, and the lithium-rich anode material relative to embodiment 1 undoped with tungsten, discharge capacity significantly improve.
The high manganese anode material Li of the rich lithium of preparation1.1Ni0.22Co0.22Mn0.47W0.01O2It is assembled into R2032 type button half-cell,
Charge and discharge cycles curve graph under the conditions of 25 DEG C, 2.0~4.6V, 1/10C is as shown in figure 3, from the figure 3, it may be seen that after circulation 50 times
The charging and discharging capacity of battery remains at 200mAh/g, has good cycle performance.
Embodiment 3~5
The high manganese anode material of rich lithium of embodiment 3,4,5 is respectively Li1.1Ni0.2Co0.1Mn0.6W0.007O2、
Li1.1Ni0.2Co0.1Mn0.6O2、Li1.1Ni0.2Co0.1Mn0.6W0.015O2, and preparation method is similar to Example 2, difference is:
The ratio of nickel cobalt manganese change and precipitant solution in be separately added into 0.7mol percentage, 0mol percentage, 1.5mol
Percentage tungsten compound Na2WO3·2H2The richness that witch culture amount is respectively 0.7mol%, 0mol%, 1.5mol% is prepared in O
The high manganese anode material Li of lithium1.1Ni0.2Co0.1Mn0.6W0.007O2、Li1.1Ni0.2Co0.1Mn0.6O2、
Li1.1Ni0.2Co0.1Mn0.6W0.015O2。
The high manganese anode material assembling of the rich lithium that the witch culture amount of preparation is respectively 0.7mol%, 0mol%, 1.5mol%
At R2032 type button half-cell, battery size is respectively #14, #19 and #153；
The witch culture amount of preparation be the high manganese anode material of 0.7mol% richness lithium half-cell #14 25 DEG C, 2.0~4.6V,
Charge-discharge test is carried out under conditions of 0.1C, 0.2C, 0.3C, 0.4C, 1.0C, 2.0C, charge-discharge performance curve graph is as shown in Figure 4
(curve in figure is corresponding in turn to the charge and discharge of 0.1C, 0.2C, 0.3C, 0.4C, 1.0C, 2.0C by the upper right corner to lower-left angular direction
Curve), as shown in Figure 4, the initial discharge voltage of battery reaches 4.5V, and battery capacity reaches 1.83Ah or more, and 2C is put
Capacitance reaches the 96.3% of 0.2C discharge capacity, and discharge-rate is high.
The witch culture amount of preparation be the high manganese anode material of 0mol% richness lithium half-cell #19 25 DEG C, 2.0~4.6V,
Charge-discharge test is carried out under conditions of 0.1C, 0.2C, 0.3C, 0.4C, 1.0C, 2.0C, charge-discharge performance curve graph is as shown in Figure 5
(curve in figure is corresponding in turn to the charge and discharge of 0.1C, 0.2C, 0.3C, 0.4C, 1.0C, 2.0C by the upper right corner to lower-left angular direction
Curve), as shown in Figure 5, although the initial discharge voltage of battery reaches 4.5V, battery capacity is below 1.82Ah.
The witch culture amount of preparation is that the half-cell ##14 and #153 of the high manganese anode material of 0.7mol%, 1.5mol% richness lithium exist
25 DEG C, 2.0~4.6V, carry out charge-discharge test under conditions of 1/10C, charge and discharge cycles curve graph is as shown in fig. 6, can by Fig. 6
Know, witch culture amount is that capacity retention rate still reaches after the half-cell of the high manganese anode material of rich lithium of 0.7mol% recycles 200 times
98%, cycle performance is good；And the half-cell that witch culture amount is the high manganese anode material of rich lithium of 1.5mol% holds after recycling 116 times
Amount retention rate straight line drops to 0.5%, and cycle performance is low.
Embodiment 6
Similar to Example 1, difference is: (1) joined 0.7mol percentage in the sulfuric acid mixed salt solution of preparation
LaNbO containing lanthanum compound3·10H2The high manganese anode material Li of rich lithium that La doped amount is 0.7mol% is prepared in O1.1Ni0.22
Co0.22Mn0.47Nb0.007O2；
The niobium of preparation is adulterated into the high manganese anode material of rich lithium or the high manganese anode material of La doped richness lithium is assembled into R2032 type knob
Half-cell is detained, carries out charge-discharge test, discharge capacity and charge-discharge cycle under conditions of 25 DEG C, 2.0~4.6V, 1/10C
Effect can be not obviously improved relative to the half-cell based on the high manganese anode material of the rich lithium of embodiment 1.
Embodiment 7
Similar to Example 1, difference is that the sulfuric acid mixed salt solution in preparation joined the Zr of 1mol percentage
(NO3)4·5H2The high manganese anode material Li of rich lithium of 0.7mol% is made in O1.1Ni0.22Co0.22Mn0.47W0.007O2。
The high manganese anode material of rich lithium that obtained zirconium doping is 0.7mol% is assembled into R2032 type button half-cell,
Charge-discharge test is carried out under conditions of 25 DEG C, 2.0~4.6V, 1/10C, discharge capacity is 185mAh/g, and electric discharge is held
Amount is not improved significantly.
Above embodiments are only preferred embodiment of the invention, are only that further detailed to technical solution of the present invention work
Description, but protection scope of the present invention and embodiment are without being limited thereto, any change done without departing from spirit of the invention
More, combination, deletion, replacement or modification etc. are included in protection scope of the present invention.
Claims (10)
1. a kind of anode material of lithium battery, which is characterized in that mix tungsten positive electrode, chemical formula Li for richness lithium Gao Meng1+δ
NiaCobMncWeO2, wherein 8=0~0.2, a=0.05~0.35, b=0.05~0.3, c=0.45~0.7, e=0.005~
0.012。
2. a kind of anode material of lithium battery according to claim 1, which is characterized in that chemical formula Li1+δ
NiaCobMncWeO2, wherein δ=0~0.2, a=0.05~0.35, b=0.05~0.3, c=0.45~0.7, e=0.005~
0.010。
3. a kind of anode material of lithium battery according to claim 1 or 2, which is characterized in that in 25 DEG C, 2.0~4.6V, 1/
Charge and discharge are carried out under conditions of 10C, discharge capacity is greater than 205mAh/g；Charge and discharge is carried out under conditions of 25 DEG C, 2.0~4.6V
Electricity, 2C discharge capacity are 96% or more of 0.2C discharge capacity.
4. the method for preparing the described in any item anode material of lithium battery of claims 1 to 3, which is characterized in that including walking as follows
It is rapid:
(1) soluble-salt of tungsten is soluble in water with precipitating reagent and be uniformly mixed, obtain precipitant mix solution；
(2) the soluble-salt mixed solution of precipitant mix solution and nickel, cobalt and manganese is added to the water carry out coprecipitation reaction, obtained
To presoma；
(3) obtained presoma and lithium compound are mixed, calcining, obtains the anode material of lithium battery.
5. the preparation method according to claim 4, which is characterized in that in step (1), the soluble-salt of the tungsten includes tungsten
One or more of sulfate, nitrate and acetate；The precipitating reagent include one of sodium carbonate and sodium hydroxide with
On；The concentration of the precipitant mix solution is 1.0~2.0mol/L.
6. the preparation method according to claim 4, which is characterized in that in step (2), the solubility of the nickel, cobalt and manganese
The concentration of mixed salt solution is 1.0~2.0mol/L；The soluble-salt of the nickel, cobalt and manganese includes the sulphur of the sulfate of nickel, cobalt
The sulfate of hydrochlorate and manganese；In the soluble-salt mixed solution of the nickel, cobalt and manganese, the molar ratio of nickel, cobalt and manganese is 0.05~
0.4: 0.05~0.3: 0.5~0.8；The total mix of the soluble-salt mixed solution of the precipitant mix solution and nickel, cobalt and manganese
It closes in solution, the molar ratio of precipitating reagent and tungsten, nickel, cobalt and the total metal of manganese is 1: 1；The temperature of the coprecipitation reaction is 50~60
DEG C, the time is 8~12 hours.
7. the preparation method according to claim 4, which is characterized in that in step (2), the general formula of the presoma is
NiqCorMnsWtCO3, wherein 0.05 < q <, 0.4,0.05 < r <, 0.3,0.5 < s <, 0.7,0 < t < 0.05.
8. the preparation method according to claim 4, which is characterized in that in step (3), the lithium compound includes lithium carbonate
One or more of with lithium hydroxide；The presoma and lithium compound rub according to tungsten, nickel, cobalt and the total metallic element of manganese and lithium
You for 1: 1.1~1: 1.3 ratio than mixing.
9. the preparation method according to claim 4, which is characterized in that in step (3), the calcining is in calcining furnace
500~650 DEG C keep the temperature 6~20 hours, keep the temperature 9~24 hours then at 750~1000 DEG C.
10. a kind of lithium ion battery, including negative electrode material, partition and electrolyte, which is characterized in that also include claims 1 to 3
Described in any item anode material of lithium battery.
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