CN105680025B - 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 PDF

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CN105680025B
CN105680025B CN201610250000.6A CN201610250000A CN105680025B CN 105680025 B CN105680025 B CN 105680025B CN 201610250000 A CN201610250000 A CN 201610250000A CN 105680025 B CN105680025 B CN 105680025B
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lithium
lithium battery
anode material
spinel nickel
anode
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CN105680025A (en
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刘辉
徐磊敏
王亮
王梦
王巍
柳娜
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Ningde Amperex Technology Ltd
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

This application involves a kind of anode material of lithium battery, the anode material of lithium battery is the spinel nickel LiMn2O4 that surface is coated with coating layer, and includes Li in the cladaBbOcAnd LiMnBO3；The structural formula of the spinel nickel LiMn2O4 is LiMx+yNi0.5‑xMn1.5‑ yO4, wherein M is selected from least one of Co, Al, Cr, Fe, Mg, Zr or Ti, 0≤x<0.2、0≤y<0.2；The LiaBbOcSpecially LiBO2、LiB3O5、LiB5O8、LiB7O11、Li2B4O7、Li3BO3、Li3B5O9、Li3B7O12、Li4B2O5Or Li4B6O11At least one of；With the compound mixed sintering of spinel nickel LiMn2O4 and boron, the cyclical stability of spinel nickel LiMn2O4 is not only increased, and inhibits the manganese dissolution of spinel nickel LiMn2O4 in the electrolytic solution.Its modified technique is suitable for all spinel nickel manganate cathode material for lithium, and simple and practicable, manufacturing cost is low, favorable reproducibility, is convenient for large-scale industrial production.

Description

A kind of anode material of lithium battery and preparation method thereof and lithium battery
Technical field
This application involves technical field of lithium ion, and in particular to a kind of anode material of lithium battery and preparation method thereof, And lithium battery.
Background technology
Lithium ion battery has energy density height, output relative to secondary cells such as traditional lead-acid battery, Ni-MH batteries Voltage is high, self discharge is low, memory-less effect and advantages of environment protection and be widely used and develop.Power and energy storage The performance of lithium ion battery critical material is the final deciding factor of battery performance, and the research of positive electrode is always science work The hot spot of author's concern.LiCoO2、LiMnO4、LiFePO4、LiNixCoyMn1-x-yO2Equal positive electrodes are widely studied. But these positive electrodes assembling lithium-ion battery system there are specific energy densities it is low, of high cost, safety is poor the defects of, it is difficult to Meet requirement of the electric vehicle to energy-storage battery.
Spinel nickel manganate cathode material for lithium is due to the advantages that its high rate performance is excellent, operating voltage is high, of low cost, and one It is directly the research hotspot of anode material for lithium-ion batteries.But spinel nickel manganate cathode material for lithium surface texture is unstable, follows The shortcomings of manganese metal during ring dissolves out seriously inhibits the large-scale application of spinel nickel manganate cathode material for lithium.
In order to develop the spinel nickel manganate cathode material for lithium haveing excellent performance, meets electric vehicle and battery high rate performance is wanted It asks, researcher, which has researched and developed, to be disclosed multiple technologies means and be modified to spinel nickel manganate cathode material for lithium.Such as,
One of method of modifying：The nickel ion doped material of aluminium hydroxide cladding is obtained by liquid phase coating, is then placed in Muffle 300~450 DEG C of nickel lithium manganate cathode materials for being thermally treated resulting in alumina-coated modification in stove, modified nickel ion doped anode The more uncoated material of material improves about 10%.
Method of modifying two：It is combined with solid phase method using sol-gel method, so that in LiNi0.5Mn1.5O4 material packets The Li covered2TiO3It is evenly distributed, final positive electrode obtained has good uniformity so that positive electrode obtained has good Cycle performance and high rate performance.
Method of modifying three：By the way that microwave susceptor zirconium oxide is added in precursor preparation process, promote reaction mass It effectively absorbs microwave to be rapidly heated to 700-950 DEG C of reaction temperature, significantly shortens the microwave firing time of product to 1-10 minutes； While nickel ion doped material is burnt at high temperature, zirconium oxide is reacted with the sources Li in nickel ion doped Surface Creation lithium ion conductor Li2ZrO3Clad is obviously improved the cycle performance and high rate performance of product.
That there are techniques is relative complex for above method, makes it difficult to carry out industrialized production, also simultaneously for manganese metal dissolution There is no corresponding method to solve, therefore, there is an urgent need for find a kind of changing for simple and practicable spinel nickel manganate cathode material for lithium at present Property method, make spinel nickel manganate cathode material for lithium that there is higher cyclical stability, and its gold in the electrolytic solution can be inhibited Belong to manganese dissolution, so as to meet the requirement of power battery.
Invention content
The application's aims to overcome that problem of the prior art, is providing a kind of spinel nickel LiMn2O4 that surface is modified just Pole material and preparation method, and material surface stable structure, the good cycling stability, and in cyclic process manganese metal do not allow it is readily soluble Go out.
The specific technical solution of the application is：
A kind of anode material of lithium battery, the anode material of lithium battery are the spinel nickel mangaic acid that surface is coated with coating layer Lithium includes Li in the cladaBbOcAnd LiMnBO3。
Preferably, the structural formula of the spinel nickel LiMn2O4 is LiMx+yNi0.5-xMn1.5-yO4, wherein M be selected from Co, Al, At least one of Cr, Fe, Mg, Zr or Ti, 0≤x<0.2、0≤y<0.2；Preferably, 0<x+y<0.2.
Preferably, the LiaBbOcSpecially LiBO2、LiB3O5、LiB5O8、LiB7O11、Li2B4O7、Li3BO3、Li3B5O9、 Li3B7O12、Li4B2O5Or Li4B6O11At least one of；More preferably LiBO2。
Preferably, wherein the LiaBbOcAnd LiMnBO3The ratio between the amount of substance be 1：0.5~4.
Preferably, the percentage that the clad accounts for the spinel nickel LiMn2O4 quality is more than zero and to be less than 3%.
Preferably, the thickness of the clad is 1~10nm.
The preparation method of the application any anode material of lithium battery before further relating to, includes the following steps：
(1) spinel nickel LiMn2O4 raw material is uniformly mixed with boron source, lithium source；
(2) anode material of lithium battery is made in mixed sintering under oxygen-containing atmosphere environment.
Preferably, in the step (1), the boron source is at least one of diboron trioxide, boric acid, lithium borate； The lithium source is at least one of lithium hydroxide, lithium carbonate, lithium borate.
Preferably, the median particle diameter D50 of the spinel nickel LiMn2O4 raw material is 3 μm~15 μm, the intermediate value of the boron source Grain size D50 is 10nm~500nm, and the median particle diameter D50 of the lithium source is 0.1 μm~5 μm.
Preferably, the addition of the boron source is the 0.1~10% of the spinel nickel LiMn2O4 feed molar number；It is described The addition of lithium source is the 0%~400% of the molal quantity of the boron source.
Preferably, the oxygen-containing atmosphere is oxygen or air, and gas flow rate is 100~5000ml/min；The mixing is burnt The heating rate of knot is 1~10 DEG C/min, 3~8h of mixed sintering at 400~800 DEG C.
The application further relates to a kind of lithium battery, including anode pole piece, cathode pole piece, be arranged at intervals at the anode pole piece and Diaphragm between cathode pole piece and electrolyte, the anode pole piece any anode material of lithium battery before containing.
Technical solution provided by the present application can reach following advantageous effect：
With the compound mixed sintering of spinel nickel LiMn2O4 and boron, the cycle for not only increasing spinel nickel LiMn2O4 is steady It is qualitative, and inhibit the manganese dissolution of spinel nickel LiMn2O4 in the electrolytic solution.Its modified technique is suitable for all spinel nickel manganese Sour lithium anode material, simple and practicable, manufacturing cost is low, favorable reproducibility, is convenient for large-scale industrial production.
Description of the drawings
Fig. 1 is spinel nickel manganate cathode material for lithium and 1 anode material of lithium battery of comparative example prepared by embodiment 1 LiNi0.5Mn1.5O4XRD diagram；
Fig. 2 is the anode material of lithium battery LiNi without sintering processes0.5Mn1.5O4SEM figure；
Fig. 3 is the SEM figures of anode material of lithium battery made from embodiment 1；
Fig. 4 is 1 positive electrode LiNi of comparative example0.5Mn1.5O4With following for anode material of lithium battery made from Examples 1 to 2 Ring stability curve.
Specific implementation mode
To keep the purpose, technical scheme and advantage of the application clearer, below in conjunction with the embodiment of the present application and attached drawing, The technical solution of the application is clearly and completely described, it is clear that described embodiment is that the application part is implemented Example, instead of all the embodiments.Based on technical solution provided by the present application and given embodiment, those skilled in the art The every other embodiment obtained without making creative work, shall fall in the protection scope of this application.
This application involves a kind of anode material of lithium battery, be the spinel nickel mangaic acid that surface is coated with one layer of clad Lithium coats one layer of clad on the surface of spinel nickel LiMn2O4；Clad includes LiaBbOcAnd LiMnBO3。
Relative to individual LiaBbOcAnd conventional oxide, LiaBbOcAnd LiMnBO3It has the advantage that：1)LiMnBO3Tool There is stable three-dimensional crystalline structure, and can be Li+Insertion/deintercalation more wide diffusion admittance is provided；2) spinel nickel The manganese of LiMn2O4 dissolves out, the mainly Mn on surface3+It is dissolved into electrolyte, and migrates to negative plate SEI films, by surface LiaBbOcAnd LiMnBO3Cladding, LiMnBO3The manganese element for stabilizing spinel nickel LiMn2O4 surface makes the Mn on surface be in and stablizes Valence state, reduce the dissolving of manganese in the electrolytic solution；3) while by surface cladding positive electrode and electrolyte is made to keep apart, When voltage is up to 5V or so in charge and discharge process, the electrolyte of electrode surface will not be oxidized decomposition and be deposited on electrode surface, subtract Electrolyte is on influences such as the dissolving of positive electrode, erosions in small charge and discharge process.
Preferably, the structural formula of spinel nickel LiMn2O4 is LiMx+yNi0.5-xMn1.5-yO4, wherein M Co, Al, Cr, Fe, At least one of Mg, Zr or Ti, 0≤x<0.2、0≤y<0.2；It is preferred that 0<x+y<0.2, more preferably 0<x+y<0.1.
As a kind of improvement of the application, a, b, c are integer, and 1≤a≤4,1≤b≤7,2≤c≤12, a+3b=2c, The i.e. described LiaBbOcSpecially LiBO2、LiB3O5、LiB5O8、LiB7O11、Li2B4O7、Li3BO3、Li3B5O9、Li3B7O12、Li4B2O5 Or Li4B6O11At least one of；Preferably LiBO2。
As a kind of improvement of the application, clad account for stratum nucleare spinel nickel LiMn2O4 quality percentage be more than zero and Less than 3%；Li in cladaBbOcAnd LiMnBO3The ratio between the amount of substance be 1：0.5~4；The thickness of clad be 1~ 10nm。
As a kind of improvement of the application, clad is by LiaBbOcWith LiMnBO3Composition, clad account for stratum nucleare spinel nickel LiMn2O4 mass ratio is less than 3%, wherein LiaBbOcAnd LiMnBO3The ratio between the amount of substance be 1：0.5~4；The thickness of clad For 1~10nm.
For clad, wherein LiaBbOcThe too high storage aerogenesis that can increase positive electrode of ratio, LiMnBO3Ratio is too high It will increase the D.C. resistance (DCR) of battery core；Clad is too thin simultaneously, effect unobvious；Clad is too thick, will increase positive electrode Polarization in charge and discharge process.
The application further relates to the preparation method of above-mentioned anode material of lithium battery, includes the following steps：
(1) spinel nickel LiMn2O4 raw material is uniformly mixed with boron source, lithium source；
(2) anode material of lithium battery is made in mixed sintering under oxygen-containing atmosphere environment.
Unstable manganese is formed during mixed sintering in boron source, lithium source and spinel nickel LiMn2O4 raw material includes LiaBbOcAnd LiMnBO3Clad so that unstable manganese occurs to shift and be stabilized in spinel nickel LiMn2O4 raw material In clad, to inhibit the manganese dissolution of spinel nickel LiMn2O4 in the electrolytic solution；Sintering process spinel nickel LiMn2O4 with Boron source and lithium source also form boron lithium composite xoide Li in clad simultaneouslyaBbOc, spinel nickel LiMn2O4 can be effectively improved Cyclical stability.The modified technique of the solid-phase sintering can be suitable for all spinel nickel manganate cathode material for lithium, simple and practicable, Manufacturing cost is low, favorable reproducibility, is convenient for large-scale industrial production.
As a kind of improvement of the application, in step (1), boron source is at least one in diboron trioxide, boric acid, lithium borate Kind；Lithium source is at least one of lithium hydroxide, lithium carbonate, lithium borate.
Preferably, the addition of the boron source is the 0.1~10% of the spinel nickel LiMn2O4 feed molar number；It is described The addition of lithium source is the 0%~400% of the molal quantity of the boron source.Wherein 0% the case where is to contain lithium simultaneously in boron source When element, at this moment boron source can provide boron and lithium simultaneously, there is no need in addition add other lithium sources, such as when boron source is lithium borate When, lithium borate functions simultaneously as boron source and lithium source.
As a kind of improvement of the application, the median particle diameter D50 of spinel nickel LiMn2O4 raw material is 3 μm~15 μm, boron source Median particle diameter D50 be 10nm~500nm, the median particle diameter D50 of lithium source is 0.1 μm~5 μm.
As a kind of improvement of the application, mixed uniformly method is ball milling, grinding or magnetic agitation etc., using ball milling, Grinding or magnetic agitation can effectively improve mixture homogeneity, be conducive to improve transformation efficiency.
As a kind of improvement of the application, oxygen-containing atmosphere is oxygen or air, and gas flow rate is 100~5000ml/min； The heating rate of mixed sintering is 1~10 DEG C/min, and the mixed sintering time is 3~8h at 400~800 DEG C；Using centainly containing Oxygen atmosphere, can effective oxygenating, while too high or too low for temperature can all cause coating thickness too thick or too thin.
The application further relates to a kind of lithium battery positive pole active substance, contains anode material of lithium battery above-mentioned.That is, the application In the active substance of lithium ion battery anode being related to, in addition to the anode material of lithium battery of the aforementioned offer of the application, however not excluded that also contain There are other ingredients that can be as active substance of lithium ion battery anode.
The application further relates to the positive active material on a kind of lithium battery anode piece, including collector and distribution collector Layer, positive electrode active material layer include lithium battery positive pole active substance above-mentioned, i.e., include lithium above-mentioned in positive electrode active material layer Cell positive material.Also contain conductive agent and binder in general positive electrode active material layer, this application involves positive electrode active material Existing conductive agent and binder can be used in conductive agent and binder in matter layer；For example, the conductive agents such as graphite, carbon nanotube； For example, the binders such as PVDF.
The application further relates to a kind of lithium ion battery, including anode pole piece, cathode pole piece, be arranged at intervals at anode pole piece and Diaphragm between cathode pole piece and electrolyte, anode pole piece are anode slice of lithium ion battery above-mentioned, i.e. anode pole piece contains There is anode material of lithium battery above-mentioned.
Examples 1 to 6 and comparative example 1~3：Spinel nickel LiMn2O4 raw material, boron source, lithium are taken by certain the ratio between amount of substance Source, be uniformly mixed, be subsequently placed in oxygen atmosphere, set gas flow rate as 5 DEG C 1000ml/min, heating rate/min, 450 DEG C sintering 5h, be made surface boron modification spinel nickel manganate cathode material for lithium；Wherein comparative example 1 is the feelings without sintering Condition；Preparation process relevant parameter is specifically as shown in table 1.
1 Examples 1 to 6 of table and comparative example 1~3 prepare modified spinelle nickel lithium manganate cathode material relevant parameter
Embodiment 7~9 and comparative example 4~7：Prepare the spinel nickel manganate cathode material for lithium of surface boron modification：With real The raw material and proportioning for applying example 6 take spinel nickel LiMn2O4 LiAl0.1Ni0.5Mn1.4O4(D50 is 10 μm), Li3BO3(D50 is 200nm) grinding uniformly mixing, then carries out solid-phase sintering reaction under different sintering conditions, and actual conditions are as shown in table 2.
4~7 reaction condition parameter list of 2 embodiment 7~9 of table and comparative example
Spinel nickel manganate cathode material for lithium and LiNi prepared by Example 10.5Mn1.5O4Respectively in X ' Pert PRO X X ray diffractometer x, step-scan, 0.02 degrees second often walk 1 second residence time, and carrying out X under the conditions of 2 10~80 ° of θ scanning ranges penetrates Line powder diffraction experiment, obtained XRD spectrum as shown in Figure 1, under the conditions of LiBO2And LiMnBO3Scanning result be also compiled in figure In 1；As can be seen from the figure contain in product X RD collection of illustrative plates and Li1Ni0.5Mn1.5O4、LiBO2And LiMnBO3Identical characteristic peak, Thus may determine that 1 solid-phase sintering of embodiment forms LiBO2And LiMnBO3；
Raw material Li Ni0.5Mn1.5O4Electron scanning micrograph as shown in Figure 2 (× 50000)；Embodiment 1 is prepared into The electron scanning micrograph of the anode material of lithium battery arrived is as shown in Figure 3 (× 30000).Comparison diagram 2 and Fig. 3 can be seen Go out, layer of substance has uniformly been coated through spinel nickel manganate cathode material for lithium made from sintering, and according to above-mentioned XRD spectrum, it should Clad substance is LiBO2And LiMnBO3, enough in spinel nickel LiMn2O4 by solid sintering technology to further demonstrate Positive electrode surface forms one layer of uniform LiBO2And LiMnBO3Clad.
Using XRD diffraction conditions same as described above, X-ray diffraction analysis, knot are carried out to Examples 1 to 9 sintered product 9 spinel nickel manganate cathode material for lithium of fruit Examples 1 to 9 forms one layer of clad on surface after sintering；By embodiment 1 ~9 and the obtained product of comparative example 1~7 carry out X-ray diffraction, and carry out qualitative and quantitative point according to obtained XRD spectrum Analysis, is as a result summarized in table 3.
Wherein, quantitative analysis method is：Clad LiaBbOcAnd LiMnBO3XRD highest peaks integral area and stratum nucleare point The ratio between XRD highest peak integral areas of spar nickel ion doped obtain clad and account for stratum nucleare molar ratio, to obtain quality percentage Than.
Positive electrode parameter list made from 3 Examples 1 to 9 of table and comparative example 1~7
Cyclical stability is tested：
The anode material of lithium battery that Example 1~9 and comparative example 1~7 are prepared is fabricated to full battery, identical Under the conditions of carry out cyclical stability test.
Test method is：Under the conditions of 25 DEG C, 4.9V is charged to using 0.5C (C is battery capacity) multiplying power, in 1.0C multiplying powers Lower electric discharge, records after recycling 200 circles, the capacity retention ratio of battery core, and test result is as shown in table 4.
The cycle-index of 1 material of Examples 1 to 2 and comparative example and the invariance curve of capacity retention ratio are as indicated at 4.From figure In as can be seen that the capacity retention ratio of material is reduced with the increase of cycle-index；It is prepared using the embodiment of the present application Surface be modified spinel nickel manganate cathode material for lithium, compared to comparative example 1 without formed contain LiBO2/LiMnBO3Cladding The spinel nickel LiMn2O4 of layer has better cyclical stability.
Mn dissolution tests：
It is molten to carry out Mn under the same conditions for the anode material of lithium battery that Example 1~9 and comparative example 1~7 are prepared Go out test.
Test method is：Material is placed on electrolyte (FEC:DMC=3:7) in, while making spinel nickel manganese therein The mass ratio of sour lithium and electrolyte is 1：10, air placement 48h is completely cut off under the conditions of 25 DEG C, takes the supernatant in electrolyte, The content of Mn elements in electrolyte is tested using inductively coupled plasma spectrum generator, carries out Mn dissolution tests, obtained survey Test result is as indicated at 4, it is seen that the anode material of lithium battery being prepared using the application condition, it is extremely low that Mn dissolves out content.
The test result of 1~7 positive electrode of 4 Examples 1 to 9 of table and comparative example
From upper table it can also be seen that relative to uncoated material, the surface-modified material formed after clad of the application Cyclical stability improves；Material nickel ion doped doping Al and Mg can effectively improve the cyclical stability of material；LiBO2Relative to LiB3O5The more excellent performance of performance；Moreover, temperature is excessively high and sintering time is too long all can accordingly cause coating thickness too Thickness reduces the cyclical stability of material.
Meanwhile it also found during the experiment, Li in cladaBbOcThe too high storage production that can increase positive electrode of ratio Gas, LiMnBO3The too high D.C. resistance (DCR) that will increase battery core of ratio；Clad is too thin simultaneously, for improving the effect of material Unobvious；Clad is too thick, will increase the polarization in positive electrode charge and discharge process.
It is not for limiting claim, any this field skill although the application is disclosed as above with preferred embodiment Art personnel can make several possible variations and modification under the premise of not departing from the application design, therefore the application Protection domain should be subject to the range that the application claim is defined.

Claims (11)

1. a kind of anode material of lithium battery, which is characterized in that the anode material of lithium battery is the point that surface is coated with coating layer Spar nickel ion doped includes Li in the cladaBbOcAnd LiMnBO3, wherein a, b, c is integer, and 1≤a≤4,1≤b≤ 7,2≤c≤12, a+3b=2c；The LiaBbOcAnd LiMnBO3The ratio between the amount of substance be 1：0.5~4；
The percentage that the clad accounts for the spinel nickel LiMn2O4 quality is more than zero and to be less than 3%；
The thickness of the clad is 1~10nm.
2. anode material of lithium battery according to claim 1, which is characterized in that the structural formula of the spinel nickel LiMn2O4 For LiMx+yNi0.5-xMn1.5-yO4, wherein M is selected from least one of Co, Al, Cr, Fe, Mg, Zr or Ti, 0≤x<0.2、0≤y <0.2。
3. anode material of lithium battery according to claim 2, which is characterized in that 0<x+y<0.2.
4. anode material of lithium battery according to claim 1, which is characterized in that the LiaBbOcSpecially LiBO2、 LiB3O5、LiB5O8、LiB7O11、Li2B4O7、Li3BO3、Li3B5O9、Li3B7O12、Li4B2O5Or Li4B6O11At least one of.
5. anode material of lithium battery according to claim 4, which is characterized in that the LiaBbOcFor LiBO2。
6. a kind of preparation method of anode material of lithium battery according to Claims 1 to 5 any claim, including it is following Step：
(1) spinel nickel LiMn2O4 raw material is uniformly mixed with boron source, lithium source；
(2) anode material of lithium battery is made in mixed sintering under oxygen-containing atmosphere environment.
7. preparation method according to claim 6, which is characterized in that in the step (1), the boron source is three oxidations At least one of two boron, boric acid, lithium borate；The lithium source is at least one of lithium hydroxide, lithium carbonate, lithium borate.
8. preparation method according to claim 7, which is characterized in that in the step (1), the spinel nickel mangaic acid The median particle diameter D50 of lithium raw material is 3 μm~15 μm, and the median particle diameter D50 of the boron source is 10nm~500nm, the lithium source Median particle diameter D50 is 0.1 μm~5 μm.
9. preparation method according to claim 7, which is characterized in that the addition of the boron source is the spinel nickel manganese The 0.1~10% of sour lithium feed molar number；The addition of the lithium source is the 0%~400% of the molal quantity of the boron source.
10. preparation method according to claim 6, which is characterized in that the oxygen-containing atmosphere is oxygen or air, gas stream Speed is 100~5000ml/min；The heating rate of the mixed sintering is 1~10 DEG C/min, mixes and burns at 400~800 DEG C 3~8h of knot.
11. a kind of lithium battery, including anode pole piece, cathode pole piece, it is arranged at intervals between the anode pole piece and cathode pole piece Diaphragm and electrolyte, which is characterized in that the anode pole piece contains any lithium battery anode of Claims 1 to 5 Material.
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