CN107768657A - A kind of anode material for lithium-ion batteries, preparation method and lithium ion battery - Google Patents
A kind of anode material for lithium-ion batteries, preparation method and lithium ion battery Download PDFInfo
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- CN107768657A CN107768657A CN201711107559.4A CN201711107559A CN107768657A CN 107768657 A CN107768657 A CN 107768657A CN 201711107559 A CN201711107559 A CN 201711107559A CN 107768657 A CN107768657 A CN 107768657A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- 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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a kind of anode material for lithium-ion batteries, its preparation method and lithium ion battery, comprise the following steps：Using the compound of transient metal Mn, lithium-containing compound as raw material, mixing, sintering, cool down, be broken, obtaining Li1+xMn2O4, then mixed, be calcined, cooled down, crushed with the additive containing M element, lithium-containing compound, dispersant, so as to obtain with Li1+xMn2O4It is shell structurre material for inner core material, the lithium compound containing M element（Ⅰ）Anode material for lithium-ion batteries.Test result indicates that in lithium ion battery formation process, lithium compound shell structurre material of the positive electrode containing M element（Ⅰ）Deviate from a part of lithium ion, form the shell structurre material with new chemical formula（Ⅱ）, the lithium ion of abjection then participates in the formation of SEI films or is embedded in the irreversible capacity that first charge-discharge is supplemented in negative pole, so that lithium ion battery has higher efficiency first.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of anode material for lithium-ion batteries, its preparation side
Method and lithium ion battery.
Background technology
The application field of lithium ion battery gradually increases, the also more and more higher of the requirement to cycle life of lithium ion battery.Just
Pole material, the capacity matching of negative material are one of key parameters in lithium ion battery design process, directly affect lithium ion
The cycle life of battery.The design capacity of usual negative material is higher than the design capacity of positive electrode by 10~15%, and this is due to
During chemical conversion, cathode interface can form the SEI films containing lithium compound, while the lithium for being partially submerged into negative pole can not take off again
Going out, participate in the normal charge and discharge cycles of lithium ion battery, the lithium ion of these consumption of chemical reaction obtains from electrolyte, or
There is provided by positive electrode.After positive electrode loss lithium ion, battery capacity can be caused to decline, coulombic efficiency reduces, cycle performance
It is deteriorated, so introducing the lithium ion being lost during new lithium source supplement chemical conversion, it is possible to improve the performance of lithium ion battery.It is this to draw
The method for entering new lithium source is exactly prelithiation, generally comprises negative pole prelithiation method and positive pole prelithiation method.
Prelithiation technique relatively common at present is negative pole prelithiation method, has both been supplemented using the technique such as lithium powder or lithium paper tinsel negative
The loss of pole irreversible capacity during initial charge.Chinese patent such as publication number CN104538591A discloses lithium ion
The prelithiation method of cell negative electrode material, described preparation method are obstructed by lithium ion on coating or coat in metallic lithium surface
Layer and/or the method for carrying out resistance value space-time to connection conductor, the embedding lithium speed and surface SEI films for regulating and controlling negative material form speed
Degree, so as to improve the coulombic efficiency of negative material, improves the cyclicity of negative material.Be oxidized because lithium metal is very easy,
And easily burn, so requirement of the technique of this prelithiation to equipment, environment is very high, which adds lithium ion battery
Cost of manufacture.
Positive pole prelithiation is to improve battery efficiency, another prelithiation method of improvement cycle performance first.As U.S. Ah
Xin Su of tribute National Laboratory et al. are proposed, in LiCoO27%Li is added in positive pole5FeO4Material, make the efficiency first of battery
14% is improved, and improves the cycle performance of battery.But account for the Li of positive electrode mass ratio 7%5FeO4After material takes off lithium
Discharge and recharge reaction is no longer participate in, the energy density of lithium ion battery can be reduced.Giulio Gabrielli of Germany et al. take
By LiNi0.5Mn1.5O4(a) positive electrode and the Li of more lithiumations1+xNi0.5Mn1.5O4The method that material is used in mixed way, by Li1+ xNi0.5Mn1.5O4Material provides extra Li during battery initial charge, makes up what negative pole was lost in process of intercalation first
Li, the Li after completely de- lithium1+xNi0.5Mn1.5O4It is converted into active LiNi0.5Mn1.5O4(b) positive electrode.This method pair
The composition of anode electrode does not influence completely, but LiNi0.5Mn1.5O4(b) material on crystal structure with directly preparing
LiNi0.5Mn1.5O4(a) certain difference be present, the cycle performance for easily causing battery is deteriorated.
The content of the invention
It is an object of the invention to provide a kind of anode material for lithium-ion batteries, preparation method and lithium ion battery, uses
The lithium ion battery of anode material for lithium-ion batteries of the present invention has higher coulombic efficiency and cycle performance.
The present invention provides a kind of anode material for lithium-ion batteries, and described anode material for lithium-ion batteries has core shell structure
Feature, its inner core material is Li1+xMn2O4, its shell structurre material (I) be the lithium compound containing M element.Described contains
The lithium compound shell structurre material (I) of M element is selected from Li2B4O7、Li3BO3、LiMg0.5Al2O4、Li4Ti5O12、Li7Ti5O12、
LiVO3、Li2VO7、Li3VO4、Li1.05Mn2O4、Li1.1Mn1.9O4、LiMnO2、Li1.2Mn0.8O2、Li2MnO3、Li5FeO4、
LiNbO3、Li3NbO8、Li2MoO4In one or more.
In battery forming process, shell structurre material (I) can provide unnecessary lithium ion and supplement negative pole to lithium ion
Consumption, while form more stable new shell structurre material (II).New shell structurre material (II) is selected from middle B2O3、
Li2B4O7、Mg0.5Al2O3.5、TiO2、Li4Ti5O12、V2O5、LiVO3、Li2VO7、LiMn2O4、Li1.2Mn0.8O2、Li2Mn4O9、
LiFeO2、Nb2O5、LiNbO3、MoO3In one or more.
The present invention provides a kind of method for preparing anode material of lithium-ion battery, comprises the following steps：
After the compound of transient metal Mn, lithium salts are well mixed, sintering, broken, classification, inner core material is obtained
Li1+xMn2O4, 0.95≤x≤1.2；By the Li1+xMn2O4With additive containing M element, lithium-containing compound, dispersant, obtain
One or more of in M element B, Mg, Al, Ti, V, Mn, Fe, Nb and Mo to mixture, dispersant is water, methanol, ethanol, more
One or more in first alcohol, higher aliphatic, Tissuemat E, OPE, polyethylene glycol and stearmide.By described in
Mixture roasting, cooling, crush, in described inner core material Li1+xMn2O4Surface forms the lithium compound shell containing M element
Rotating fields material (I), obtains anode material for lithium-ion batteries of the present invention；
The compound of the transient metal Mn is selected from manganese sulfate, manganese carbonate, manganese nitrate, manganese chloride, manganese oxalate, titanium dioxide
One or more in manganese, manganese sesquioxide managnic oxide and mangano-manganic oxide；Preferably, the compound of transient metal Mn be selected from manganese carbonate,
One or more in manganese dioxide, manganese sesquioxide managnic oxide and mangano-manganic oxide；It is furthermore preferred that the compound of transient metal Mn is selected from
One or more in manganese dioxide and mangano-manganic oxide.
The lithium-containing compound in lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium chloride and lithium fluoride one
Kind is several；Preferably, one or more of the lithium-containing compound in lithium hydroxide, lithium carbonate and lithium fluoride.
The additive containing M element be selected from boride alloy, compound containing Mg, compound containing Al, compound containing Ti, containing Vization
One or more in compound, compound containing Mn, compound containing Fe, compound containing Nb and compound containing Mo；Preferably, it is described to contain
The one kind of M element additive in boride alloy, compound containing Ti, compound containing V, compound containing Fe and compound containing Mo
It is or a variety of.
The dispersant is selected from water, methanol, ethanol, polyalcohol, higher aliphatic, Tissuemat E, OPE, poly-
One or more in ethylene glycol and stearmide；Preferably, the dispersant is selected from water, ethanol, polyalcohol, higher aliphatic
One or more in alcohol, polyethylene glycol and stearmide.
Described sintering temperature is 650 DEG C~1100 DEG C, and described sintering time is 1 hour~60 hours.Preferably, institute
The sintering temperature stated is 800 DEG C~1000 DEG C, and described sintering time is 10 hours~36 hours.
Described sintering temperature is 250 DEG C~900 DEG C, and described sintering time is 1 hour~48 hours.Preferably, institute
The sintering temperature stated is 300 DEG C~750 DEG C, and described sintering time is 2 hours~18 hours.
The additive M and Li1+xMn2O4The mol ratio of particle is (0.001~0.5):1.Preferably, the additive M
With Li1+xMn2O4The mol ratio of particle is (0.05~0.1):1
The dispersant and Li1+xMn2O4The mol ratio of particle is (0.001~10):1.Preferably, the dispersant with
Li1+xMn2O4The mol ratio of particle is (0.1~2):1.
The present invention provides a kind of lithium ion battery, including anode material for lithium-ion batteries described above.
The present inventor has found that following reaction occurs in formation process for lithium ion battery of the present invention by studying：
Shell structurre material (I) deviates from part or all of lithium ion and forms shell structurre material (II), and the lithium ion of abjection is in negative pole
Inner core material Li embedded or in negative terminal surface formation SEI films, positive electrode1+xMn2O4Crystal structure do not send out
It is raw to change；Shell structurre material (II) is converted into and inner core material Li1+xMn2O4Protective layer, or formed with kernel knot
Structure material Li1+xMn2O4Mutually compound other kinds of positive electrode participates in the charge and discharge cycles reaction of lithium ion battery.
The present inventor is had found by studying, and by the selection application of dispersant, can will be contained M element additive and equably be divided
It is dispersed in inner core material Li1+xMn2O4Surface, be can be obtained by by being simply calcined with shell structurre material (I)
Anode material for lithium-ion batteries.
The method of this prelithiation, anode material for lithium-ion batteries caused by avoiding lithium ion loss are deteriorated, improved
The coulombic efficiency of lithium ion battery, significantly improve the cycle performance of lithium ion battery.
Test result indicates that after lithium ion battery uses anode material for lithium-ion batteries of the present invention, it is possible to increase
The coulombic efficiency of lithium ion battery, the cycle performance for improving lithium ion battery.The method of this prelithiation does not increase lithium ion
The cost of manufacture of battery, the energy density of lithium ion battery is not reduced, be adapted to large-scale application.
Technical scheme is not limited to LiMn2O4, in addition to cobalt acid lithium, lithium nickelate, nickle cobalt lithium manganate, nickel mangaic acid
Lithium, lithium nickel cobalt dioxide, nickel cobalt lithium aluminate, nickel manganese lithium aluminate, more lithium manganese cathode materials, ferric metasilicate lithium, manganese silicate of lithium, cobaltous silicate
One or more in lithium, lithium vanadate, lithium titanate, LiFePO4, lithium manganese phosphate and phosphoric acid vanadium lithium, institute of the present invention can be passed through
The preparation method stated obtains the lithium ion battery material with core shell structure, and the shell structure material of prelithiation is in lithium ion battery
Deviate from part or all of lithium ion during, realize the effect for improving battery coulombic efficiency, improving cycle performance of battery.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is positive electrode (the i.e. embodiment of the present invention in battery before and after the lithium ion battery chemical conversion of the embodiment of the present invention 11
1) schematic diagram of structure change；
Fig. 2 is the cycle performance of lithium ion battery curve ratio relatively figure of the embodiment of the present invention 11 and comparative example 2.
Embodiment
In order to further illustrate the present invention, with reference to embodiments to a kind of lithium ion cell positive material provided by the invention
Material, its preparation method and lithium ion battery are described in detail, but can not be understood as limiting the scope of the present invention.
Embodiment 1
By MnO2And Li2CO3According to mol ratio 1：0.25 is well mixed, is sintered 18 hours at 850 DEG C, natural cooling, breaks
Inner core material LiMn is obtained after broken, classification2O4；Then by LiMn2O4With H3BO3, LiOH, water, ethanol is according to mol ratio 1：
0.002：0.001：2：0.5 is well mixed, is calcined 12 hours at 550 DEG C, natural cooling, crushes, after classification, obtains inner core
Material is LiMn2O4, shell structurre material be Li2B4O7Anode material for lithium-ion batteries.
Embodiment 2
By Mn3O4With LiOH according to mol ratio 1：1.5 is well mixed, is sintered 24 hours at 680 DEG C, natural cooling, crush,
Inner core material LiMn is obtained after classification2O4；Then by LiMn2O4With Li OH, nano-MgO, nanometer Al2O3, polyethylene glycol presses
According to mol ratio 1：0.002：0.001：0.002：0.1 is well mixed, is calcined 8 hours at 450 DEG C, natural cooling, crushes, after classification
It is LiMn to obtain inner core material2O4, shell structurre material be LiMg0.5Al2O4Anode material for lithium-ion batteries.
Embodiment 3
By MnO2With LiOH according to mol ratio 1：0.52 is well mixed, is sintered 20 hours at 900 DEG C, natural cooling, crush,
Inner core material Li is obtained after classification1.04Mn2O4；Then by Li1.04Mn2O4With LiOH, titanium tetrachloride, OPE,
Stearmide is according to mol ratio 1：0.007：0.005：0.001：0.5 is well mixed, is calcined 6 hours at 600 DEG C, natural cooling,
It is Li to obtain inner core material after broken, classification1.04Mn2O4, shell structurre material be Li7Ti5O12Lithium ion cell positive
Material.
Embodiment 4
By MnCO3And Li2CO3According to mol ratio 1：0.245 is well mixed, is sintered 36 hours at 830 DEG C, natural cooling, breaks
Inner core material Li is obtained after broken, classification0.98Mn2O4；Then by Li0.98Mn2O4With Li2CO3、V2O5, ethanol, higher aliphatic
Alcohol is according to mol ratio 1：0.004：0.002：2：0.5 is well mixed, is calcined 10 hours at 350 DEG C, natural cooling, crushes, classification
Inner core material is Li afterwards0.98Mn2O4, shell structurre material be Li2VO7Anode material for lithium-ion batteries.
Embodiment 5
By MnO2And Li2CO3According to mol ratio 1：0.26 is well mixed, is sintered 12 hours at 950 DEG C, natural cooling, breaks
Inner core material Li is obtained after broken, classification1.04Mn2O4；Then by Li1.04Mn2O4With Li2CO3、Mn(OH)2, polyethylene glycol and
Stearmide is according to mol ratio 1：0.011：0.019：0.02：0.1 is well mixed, is calcined 15 hours at 650 DEG C, natural cooling,
Inner core material is Li after broken, classification1.04Mn2O4, shell structurre material be Li1.1Mn1.9O4Lithium ion cell positive material
Material.
Embodiment 6
By MnCO2With LiOH according to mol ratio 1：0.51 is well mixed, is sintered 10 hours at 925 DEG C, natural cooling, breaks
Inner core material Li is obtained after broken, classification1.02Mn2O4；Then by Li1.02Mn2O4With LiOH, FeNO3, water, polyethylene glycol press
According to mol ratio 1：0.15：0.01：2：0.5 is well mixed, is calcined 2 hours at 350 DEG C, natural cooling, crushes, kernel knot after classification
Structure material is Li1.02Mn2O4, shell structurre material be Li5FeO4Anode material for lithium-ion batteries.
Embodiment 7
By MnO2And Li2CO3According to mol ratio 1：0.275 is well mixed, is sintered 16 hours at 1000 DEG C, natural cooling, breaks
Inner core material Li is obtained after broken, classification1.05Mn2O4；Then Li1.05Mn2O4With by LiOH, niobium oxalate, polyalcohol, advanced fat
Fat alcohol is according to mol ratio 1：0.03：0.01：3：0.2 is well mixed, is calcined 6 hours at 900 DEG C, natural cooling, crushes, after classification
Inner core material is Li1.05Mn2O4, shell structurre material be Li3NbO8Anode material for lithium-ion batteries.
Embodiment 8
By Mn3O4With LiOH according to mol ratio 1：0.52 is well mixed, is sintered 18 hours at 950 DEG C, natural cooling, crush,
Inner core material Li is obtained after classification1.1Mn2O4；Then by Li1.1Mn2O4With LiOH, MoO3, OPE according to mole
Than 1：0.03：0.015：0.02 is well mixed, is calcined 12 hours at 800 DEG C, natural cooling, crushes, inner core material after classification
Expect for Li1.1Mn2O4, shell structurre material be Li2MoO4Anode material for lithium-ion batteries.
Embodiment 9
By MnO2With LiOH according to mol ratio 1：0.53 is well mixed, is sintered 26 hours at 780 DEG C, natural cooling, crush,
Inner core material Li is obtained after classification1.06Mn2O4；Then by Li1.06Mn2O4With LiOH, Nb2O5, magnesium nitrate, Al (OH)3, it is poly-
Divinyl, stearmide are according to mol ratio 1：0.04：0.01：0.01：0.04：0.1：0.3 is well mixed, and 18 are calcined at 750 DEG C
Hour, natural cooling, crush, inner core material is Li after classification1.06Mn2O4, shell structurre material be 0.5LiMg0.5Al2O4﹒
0.5LiNbO3Anode material for lithium-ion batteries.
Embodiment 10
By MnO2And Li2CO3According to mol ratio 1：0.2575 is well mixed, is sintered 20 hours at 900 DEG C, natural cooling, breaks
Inner core material Li is obtained after broken, classification1.03Mn2O4；Then by Li1.03Mn2O4With Li2CO3、Mn3O4、MgO2、Al2O3, second
Alcohol, OPE are according to mol ratio 1：0.053：0.038：0.02：0.04：1：1 is well mixed, small in 900 DEG C of roastings 10
When, natural cooling, crush, classification inner core material is Li1.04Mn2O4, shell structurre material be 0.6Li1.1Mn1.9O4﹒
0.4LiMg0.5Al2O4Anode material for lithium-ion batteries.
Comparative example 1
By MnO2And Li2CO3According to mol ratio 1：0.25 is well mixed, is sintered 18 hours at 850 DEG C, natural cooling, breaks
LiMn is obtained after broken, classification2O4Anode material for lithium-ion batteries.
Embodiment 11
By obtained anode material for lithium-ion batteries, electrically conductive graphite, acetylene black, Kynoar and N- first in embodiment 1
Base pyrrolidones is at normal temperatures and pressures according to mass ratio 93：0.15：0.15：0.4：200 are mixed to form slurry, are coated uniformly on aluminium
Positive plate is made in paper tinsel surface.Above-mentioned pole piece is dried at 120 DEG C, according to 2.9g/cm-1Compacted density roll-in after, be cut into
Rectangular anode pole piece, the cathode pole piece of corresponding size is made using carbonaceous mesophase spherules as negative pole, with 1mol/L LiPF6's
Ethylene carbonate (EC) and dimethyl carbonate (DMC) solution are electrolyte, and wherein EC and DMC volume ratio are 1：1, then filling
The lithium ion battery of 18650 type 1300mAh capacity is assembled into the glove box of full argon gas.
Embodiment 12-20
By obtained anode material for lithium-ion batteries in embodiment 2~10, electrically conductive graphite, acetylene black, Kynoar and
1-METHYLPYRROLIDONE is at normal temperatures and pressures according to mass ratio 93：0.15：0.15：0.4：200 are mixed to form slurry, uniformly coating
Positive plate is made in aluminium foil surface.Above-mentioned pole piece is dried at 120 DEG C, according to 2.9g/cm-1Compacted density roll-in after, cut out
Rectangular anode pole piece is cut into, the cathode pole piece of corresponding size is made using carbonaceous mesophase spherules as negative pole, with 1mol/L's
LiPF6Ethylene carbonate (E C) and dimethyl carbonate (DMC) solution be electrolyte, wherein EC and DMC volume ratio are 1：1,
Then the lithium ion battery of 18650 type 1300mAh capacity is assembled into the glove box full of argon gas.
Comparative example 2
By obtained anode material for lithium-ion batteries, electrically conductive graphite, acetylene black, Kynoar and N- first in comparative example 1
Base pyrrolidones is at normal temperatures and pressures according to mass ratio 93：0.15：0.15：0.4：200 are mixed to form slurry, are coated uniformly on aluminium
Positive plate is made in paper tinsel surface.Above-mentioned pole piece is dried at 120 DEG C, according to 2.9g/cm-1Compacted density roll-in after, be cut into
Rectangular anode pole piece, the cathode pole piece of corresponding size is made using carbonaceous mesophase spherules as negative pole, with 1mol/L LiPF6's
Ethylene carbonate (EC) and dimethyl carbonate (DMC) solution are electrolyte, and wherein EC and DMC volume ratio are 1：1, then filling
The lithium ion battery of 18650 type 1300mAh capacity is assembled into the glove box of full argon gas.
The present invention tests the coulombic efficiency first of embodiment 11-20 and the lithium ion battery in comparative example 2, as a result such as table
Shown in 1.
The coulombic efficiency first of the embodiment 11~20 of table 1 and the lithium ion battery in comparative example 2
Capacity is protected after the present invention tests the circulation circulation in 200 weeks of embodiment 11-20 and the lithium ion battery in comparative example 2
Holdup, as a result as described in Table 2.
Capability retention after circulations in 200 weeks of the embodiment 11~20 of table 2 and the lithium ion battery in comparative example 2
Fig. 2 is 400 weeks specific discharge capacity comparison curves of circulation of embodiment 11 and the lithium ion battery in comparative example 2.Its
Middle curve 1 is the cycle performance curve of the lithium ion battery of embodiment 11, and after circulation in 400 weeks, battery capacity conservation rate is
94.9%.Curve 2 is the cycle performance curve of the lithium ion battery of comparative example 2, and after circulation in 400 weeks, battery capacity conservation rate is
86.6%.As shown in Figure 2, it is that the cycle performance of lithium ion battery that anode material for lithium-ion batteries makes is more excellent with embodiment 11.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of anode material for lithium-ion batteries, it is characterised in that described anode material for lithium-ion batteries has core shell structure
Feature, its inner core material is Li1+xMn2O4, its shell structurre material (I) be made up of the lithium compound containing M element, it is described
The lithium compound shell structurre material containing M element be selected from Li2B4O7、Li3BO3、LiMg0.5Al2O4、Li4Ti5O12、Li7Ti5O12、
LiVO3、Li2VO7、Li3VO4、Li1.05Mn2O4、Li1.1Mn1.9O4、LiMnO2、Li1.2Mn0.8O2、Li2MnO3、Li5FeO4、
LiNbO3、Li3NbO8、Li2MoO4In one or more, described x scope, 0.95≤x≤1.2.
2. anode material for lithium-ion batteries according to claim 1, it is characterised in that use the lithium ion cell positive material
The lithium ion battery of material is in formation process, lithium compound shell structurre material (I) of the anode material for lithium-ion batteries containing M element
Deviate from a part of lithium ion, form the shell structurre material (II) with new chemical formula.
3. anode material for lithium-ion batteries according to claim 2, it is characterised in that the shell of described new chemical formula
Structural material (II), selected from B2O3、Li2B4O7、Mg0.5Al2O3.5、TiO2、Li4Ti5O12、V2O5、LiVO3、Li2VO7、LiMn2O4、
Li1.2Mn0.8O2、Li2Mn4O9、LiFeO2、Nb2O5、LiNbO3、MoO3In one or more.
4. anode material for lithium-ion batteries according to claim 1, it is characterised in that described shell structurre material (I)
For Li2B4O7、Li3BO3、LiMg0.5Al2O4、Li7Ti5O12、Li2VO7、Li3VO4、Li1.1Mn1.9O4、Li5FeO4、LiNbO3、
Li3NbO8、Li2MoO4In one or more.
5. anode material for lithium-ion batteries according to claim 1, it is characterised in that described shell structurre material (I)
For Li3BO3、LiMg0.5Al2O4、Li1.1Mn1.9O4、Li5FeO4、Li3NbO8、Li2MoO4In one or more.
6. anode material for lithium-ion batteries according to claim 2, it is characterised in that the shell of described new chemical formula
Structural material (II), selected from B2O3、Li2B4O7、Mg0.5Al2O3.5、Li2Mn4O9、LiFeO2、LiNbO3、MoO3In one kind or more
Kind.
7. the preparation method of anode material for lithium-ion batteries according to claim 1, it is characterised in that including following step
Suddenly：
After the compound of transient metal Mn, lithium-containing compound are well mixed by step a), sintering, broken, classification, kernel knot is obtained
Structure material Li1+xMn2O4, 0.95≤x≤1.2；
Step b) is by the Li1+xMn2O4With the additive containing M element, lithium-containing compound, dispersant, mixture is obtained；
The mixture is calcined, cooled down, be broken by step c), obtains anode material for lithium-ion batteries of the present invention.It is special
Sign is that inner core material is Li1+xMn2O4, shell structurre material (I) be the lithium compound containing M element.
8. preparation method according to claim 7, it is characterised in that the dispersant is selected from water, methanol, ethanol, polynary
One or more in alcohol, higher aliphatic, Tissuemat E, OPE, polyethylene glycol and stearmide.
9. preparation method according to claim 7, it is characterised in that the additive containing M element and Li1+xMn2O4Rub
Your ratio is (0.001~0.5): 1；The dispersant and Li1+xMn2O4Mol ratio be (0.001~10): 1.
10. a kind of lithium ion battery, it is characterised in that usage right requires the lithium ion cell positive material described in 1 to 6 any one
Expect the lithium ion battery made.
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