CN110148712A - A kind of rich lithium manganese anode material and preparation method thereof that compound coating is modified - Google Patents
A kind of rich lithium manganese anode material and preparation method thereof that compound coating is modified Download PDFInfo
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Abstract
The invention discloses a kind of modified rich lithium manganese anode materials and preparation method thereof of compound coating, which includes the composite oxides of matrix and matrix outer cladding；Composite oxides are the composite oxides of Li, B and metal Me, and metal Me is at least one of Al, Zr etc..The preparation method is mixed the following steps are included: rich lithium manganese positive electrode active materials matrix is added in deionized water, is filled with CO2Gas；The salting liquid A of preparing metal Me；Prepare the solution B of boron compound；Solution A, B are added into above-mentioned active material matrix mixed liquor；It is in neutrality mixed solution or alkalescent, heating obtains colloidal mixture；Colloidal mixture is uniformly wrapped on matrix surface in the molten state；Products therefrom is dry, grinding, constant temperature heat treatment obtain the modified rich lithium manganese anode material of compound coating.The present invention can overcome in existing product the deficiencies of poor remnants Li too high levels, high rate performance, poor circulation.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof, and in particular to a kind of compound coating is modified
Rich lithium manganese anode material and preparation method thereof.
Background technique
Rich lithium manganese anode material specific capacity with higher, but its first charge discharge efficiency is relatively low, high rate performance is poor, cycle performance
Difference, the very fast disadvantage of capacity attenuation limit its development, therefore, seek one kind and can effectively promote rich lithium manganese anode material to imitate for the first time
Rate, high rate performance, the modification mode of cyclical stability and preparation method are imperative.
To promote material discharging capacity and material high rate performance, generallys use and material surface is handled, promote material
Activity；To promote positive electrode cyclical stability, cladding processing usually is carried out to positive electrode surface.Traditional method for coating master
Will there are two types of: one is dry method claddings, directly by positive electrode matrix and cladding substance dry mixed after high-temperature heat treatment, formed
Clad.But dry method is coated with obvious shortcoming, and because cladding content of material is relatively fewer, dispersing uniformity not can guarantee, and
Material surface remains Li2CO3And the problem of LiOH, is not resolved, impacts to the high-temperature behavior of material.Another is wet
Method cladding, high-temperature heat treatment after positive electrode matrix is mixed, dried with the solution of cladding substance, forms clad.It is wet
Being evenly coated property of method increases compared with dry method cladding, but solvent seasoning process will cause partial enclosure matter and be deposited on clad table
Face, clad uniformity are affected.Li simultaneously2CO3It is slightly soluble in water, the characteristic insoluble in Conventional solvents such as ethyl alcohol, acetone makes
The residual lithium problem in positive electrode surface still fails to be effectively improved.
Therefore, a kind of novel coating modification method need to be developed, while being effectively improved positive electrode surface-active, is promoted
Material high rate performance and cycle performance.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the material residues Li content mistake mentioned in background above technology
High, the deficiencies of high rate performance is poor, poor circulation and defect, provide a kind of compound coating modification rich lithium manganese anode material and its
Preparation method.
In order to solve the above technical problems, technical solution proposed by the present invention is a kind of modified rich lithium manganese anode of compound coating
Material, the richness lithium manganese anode material includes rich lithium manganese positive electrode active materials matrix and the combined oxidation for being coated on matrix surface
Object；The composite oxides are the composite oxides of Li, B and metal Me, and the metal Me is one in Al, Ti, Zr, Mg, W
Kind is a variety of.The Li of composite oxides is dissolved from surface residual TSL herein.
The modified rich lithium manganese anode material of above-mentioned compound coating, it is preferred that point of the richness lithium manganese positive electrode active materials
Minor is represented by xLi2MnO3 (1-x) LiMO2, and wherein M is at least one of Ni, Co, Mn, Fe, Cr, and 0.1≤x≤
0.9。
The modified rich lithium manganese anode material of above-mentioned compound coating, it is preferred that the Li in the composite oxides is derived from
The remaining Li of the matrix surface of the richness lithium manganese positive electrode active materials2CO3, LiOH and free state lithium ion.
The modified rich lithium manganese anode material of above-mentioned compound coating, it is preferred that B element content accounts in the composite oxides
0.01wt%~1wt% of entire richness lithium manganese anode material, metal Me account for entire rich lithium manganese anode material 0.05%~
0.3%.
As a general technical idea, the present invention also provides a kind of preparation method of above-mentioned rich lithium manganese anode material,
The following steps are included:
(1) rich lithium manganese positive electrode active materials matrix is added in deionized water according to mass ratio 1:2~1:5, is mixed.
And CO is slowly filled in mixed liquor2Gas.This step is the micro- acidification in surface to rich lithium manganese positive electrode active materials, together
When promote surface residual lithium compound and/or free state lithium ion sufficiently to dissolve in acid condition；
(2) soluble metallic salt of metal Me is dissolved in solvent, stirs evenly to obtain solution A；
(3) boron compound is dissolved in solvent, stirs evenly to obtain solution B；
(4) solution A, B is added into above-mentioned steps (1) resulting mixed liquor, be uniformly mixed, make metal Me ion,
Li ion and boracic uniform ion are scattered in mixed solution；
(5) ammonium hydroxide is gradually instilled into above-mentioned steps (4) gained mixed solution, adjusting pH value (preferably 7.0-8.0) makes to mix
Conjunction solution is in neutrality or alkalescent, prevents from being further acidified material surface in heating process；Meanwhile the mixed solution being existed
It is heated under the conditions of 60 DEG C~80 DEG C, until solution loses flowability, obtains colloidal mixture；
(6) colloidal mixture for obtaining above-mentioned steps (5) is mixed under the conditions of 160 DEG C~220 DEG C, make its
The material surface of described matrix is uniformly wrapped under molten condition；
(7) above-mentioned steps (6) products therefrom is dry, grinding, then at 300 DEG C~700 DEG C constant temperature heat treatment 4~
10h obtains the rich lithium manganese anode material of the micro- acidification in surface and compound coating modification.
In above-mentioned preparation method of the invention, by carrying out micro- acidification to material surface, remained on surface can be promoted
Lithium carbonate, lithium hydroxide etc. (TSL) sufficiently dissolve, be effectively reduced the residual Li content of rich lithium manganese anode material, and with B, metal
Me forms composite oxides clad, provides lithium source for compound coating layer.Simultaneously by carrying out micro- acidification to material surface,
The activity of material surface can be also promoted, improves material surface electric conductivity, while improving cyclical stability, effect can pass through electricity
The first charge discharge efficiency of performance test is evaluated.
Above-mentioned preparation method, preferred: the solvent is at least one of water, ethyl alcohol；
Above-mentioned preparation method, preferred: in the step (1), every liter of mixed liquor CO2Gas be filled with speed be 10~
100ml/min, inflation incorporation time are 1~15min；
Above-mentioned preparation method, preferred: in the step (2), soluble metallic salt and solvent are by 1:10~1:50
Mass ratio be configured to solution A.
Above-mentioned preparation method, it is preferred: in the step (3), the boron compound be boron oxide and boric acid at least
One kind, the boron compound and solvent are to be configured to solution B by the mass ratio of 1:10~1:50.
Above-mentioned preparation method, preferred: in the step (4), the time of mixing is controlled in 1~10min；It is described
In step (5), (6), the time of mixing is controlled in 10~60min.
Above-mentioned technical proposal of the invention is based primarily upon following principle: carrying out first to rich lithium manganese surface of positive electrode active material
Processing, the CO being filled with2Gas can be reacted with deionized water, keep mixed liquor weakly acidic, made material surface slightly sourization, promoted simultaneously
The dissolution of the remaining lithium compound and free state Li of matrix surface and gap location；By controlling CO2Gas intake and
Incorporation time, controllable control surface slightly sourization degree, regulates and controls material surface activity, can also realize Li content residual to product
Control.Lithium, boron, metal Me are uniformly wrapped on rich lithium manganese surface of positive electrode active material by process means again and form combined oxidation
Object clad reduces reacting for rich lithium manganese positive electrode active materials and electrolyte in charge and discharge process in this way.In addition, clad
In lithium derive from the rich remaining Li of lithium manganese surface of positive electrode active material2CO3, LiOH and free state Li, metal Me then include Al,
At least one of Mg, Zr, Ti, W, finally formed lithium-contained composite oxide is a kind of good lithium ion conductor in clad
Material has preferable Li compared with simple oxide material+Passage capacity can not only improve the cycle performance of positive electrode
And high rate performance, and to Li+Insertion and abjection influence it is smaller；And the fusant that boron-containing compound is formed at low temperature, it can
The fusion of lithium, boron, metal Me compound is further speeded up, the uniformity of compound coating layer is improved.As it can be seen that rich lithium manganese of the invention
The composite oxides of positive electrode active materials matrix outer cladding absorb the advantage of various technological means, and achieve synergy
Remarkable result.
Compared with prior art, preparation method of the invention has following clear superiority:
(1) the method for the present invention, which passes through, is filled with CO into basis material and deionized water mixed liquor2Gas makes mixed liquor in weak
Acidity carries out micro- acidification to matrix surface, promotes matrix surface residual lithium compound and the abundant dissolution of free state Li,
It is effectively improved rich lithium manganese anode material surface state simultaneously, material surface activity is promoted, to promote material discharge capacity for the first time
And efficiency.And by CO2The control of gas intake and incorporation time controls surface slightly sourization degree, can also realize
The control of Li content residual to product.
(2) the method for the present invention can be made with equally distributed lithium, boron, composite oxide of metal clad rich lithium manganese just
Pole material, wherein the Li in compound coating layer is directly using from rich lithium manganese anode material Li remained on surface2CO3, LiOH with
And free state Li.
(3) the method for the present invention is by coating substance being stirred under watery fusion state in step (6), make lithium, boron,
Metal Me composite oxides are uniformly mixed, and are formed clad, are closely coated on rich lithium manganese surface of positive electrode active material.
(4) the method for the present invention effectively improves material surface property, and product first charge-discharge efficiency is promoted, and compound
Oxide cladding layers have preferable electric conductivity, effectively reduce cladding bring capacitance loss, improve the forthright again of material
Energy.Comparing the subsequent embodiment and comparative example 1,2,3 of the present invention can be seen that, the electric discharge for the first time of rich lithium manganese anode material of the invention
Specific capacity improves 5~10mAh/g relative to traditional covering material, and 1C/0.2C multiplying power promotes 1%~3%.
(5) composite oxides clad made from the method for the present invention has good chemical stability, it is suppressed that positive material
The generation of material and electrolyte contacts side reaction, avoids deterioration of the positive electrode substance in cyclic process, improves battery
Stable circulation, comparative example 1,2,3 and comparative example 1,2,3 can be seen that, recycle within the present invention richness lithium manganese anode material 50 weeks
Capacity retention ratio improves 3%~5% relative to traditional covering material.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Marginal data
Fig. 1 is the micro- electromicroscopic photograph of the basis material of rich lithium manganese anode material in the embodiment of the present invention 1.
Fig. 2 is the micro- electromicroscopic photograph for the rich lithium manganese anode material that compound coating is modified in the embodiment of the present invention 1.
Fig. 3 is the micro- electromicroscopic photograph for the rich lithium manganese anode material that compound coating is modified in the embodiment of the present invention 2.
Fig. 4 is the micro- electromicroscopic photograph for the rich lithium manganese anode material that compound coating is modified in the embodiment of the present invention 3.
Compared with basis material FE-SEM, 1/2/3 photo grain corner of embodiment is rounder and more smooth, and between particle gap by glass
State composite oxides are filled, and complete clad is formed, and are conducive to the improvement of material circulation performance.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of rich lithium manganese anode material that the micro- acidification in surface and compound coating of the invention as shown in Figure 2 are modified, packet
Include the composite oxides of rich lithium manganese positive electrode active materials matrix (referring to Fig. 1) and matrix outer cladding；The glassy state combined oxidation
Object is the composite oxides of Li, B and Al, and the molecular formula of rich lithium manganese positive electrode active materials is represented by the present embodiment
0.5Li2MnO3·0.5LiNi0.5Mn0.5O2.Li in composite oxides derives from the matrix surface of rich lithium manganese positive electrode active materials
Remaining Li2CO3, LiOH and free state lithium ion.In the present embodiment, B element content is accounted for entirely in glassy state composite oxides
The 0.08wt% of rich lithium manganese anode material, metal Al account for the 0.06% of entire rich lithium manganese anode material.
The preparation method for the rich lithium manganese anode material that the micro- acidification in the above-mentioned surface of the present embodiment and compound coating are modified,
Specifically includes the following steps:
(1) by 1000g 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Uncoated rich lithium manganese positive electrode active materials matrix,
It is added in 3L deionized water, is stirred 5min.Then 50ml/min rate is slowly filled with CO2, 10min is mixed；
(2) 8.342g ANN aluminium nitrate nonahydrate is dissolved in 150mL deionized water, is mixed evenly, obtain metal salt solution；
(3) 4.576g boric acid is dissolved in 150mL deionized water, is mixed evenly, obtain boric acid solution；
(4) metal salt solution and boric acid solution of above-mentioned preparation are slowly added in step (1) resulting mixed solution,
Accelerate stirring 5min, is mixed evenly；
(5) it being slowly dropped into ammonium hydroxide in step (4) resulting mixed solution, pH value of solution to be mixed is stablized at 7.0~8.0,
20min is mixed；By gained mixture, heating stirring obtains mixture when mixture loses flowability under the conditions of 80 DEG C
Colloidal sol；
(6) the resulting mixture colloidal sol of step (5) is mixed in 180 DEG C of oil baths, heating mixing time is
30min；
(7) it after step (6) products therefrom is dry, grinding is crushed, is placed in sintering furnace and is heat-treated, 600 DEG C of constant temperature
Rich lithium manganese anode material 8h modified to get the micro- acidification in surface as shown in Figure 2 and compound coating.
As it can be seen that compared with basis material, 1 product photo grain corner of the embodiment of the present invention is rounder and more smooth by comparison diagram 1 and Fig. 2,
And gap is filled by glassy state composite oxides between particle, forms complete clad, is conducive to changing for material circulation performance
It is kind.
Embodiment 2:
A kind of rich lithium manganese anode material that the micro- acidification in surface and compound coating of the invention as shown in Figure 3 are modified, packet
Include the composite oxides of rich lithium manganese positive electrode active materials matrix and matrix outer cladding；The glassy state composite oxides be Li, B and
The composite oxides of Al, the molecular formula of rich lithium manganese positive electrode active materials is represented by 0.5Li in the present embodiment2MnO3·
0.5LiNi0.5Mn0.5O2.Li in composite oxides derives from the remnants of the matrix surface of rich lithium manganese positive electrode active materials
Li2CO3, LiOH and free state lithium ion.In the present embodiment, B element content accounts for entire rich lithium manganese in glassy state composite oxides
The 0.08wt% of positive electrode, metal Al account for the 0.06% of entire rich lithium manganese anode material.
The preparation method for the rich lithium manganese anode material that the micro- acidification in the above-mentioned surface of the present embodiment and compound coating are modified,
Specifically includes the following steps:
(1) by 1000g 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Uncoated rich lithium manganese positive electrode active materials matrix,
It is added in 3L deionized water, is stirred 5min.Then 50ml/min rate is slowly filled with CO2, 10min is mixed；
(2) 8.342g ANN aluminium nitrate nonahydrate is dissolved in 150mL dehydrated alcohol, is mixed evenly, obtain metal salt solution；
(3) 4.576g boric acid is dissolved in 150mL dehydrated alcohol, is mixed evenly, obtain boric acid solution；
(4) metal salt solution and boric acid solution of above-mentioned preparation are slowly added in step (1) resulting mixed solution,
Accelerate stirring 5min, is mixed evenly；
(5) it being slowly dropped into ammonium hydroxide in step (4) resulting mixed solution, pH value of solution to be mixed is stablized at 7.0~7.5,
20min is mixed；By gained mixture, heating stirring obtains mixture when mixture loses flowability under the conditions of 80 DEG C
Colloidal sol；
(6) the resulting mixture colloidal sol of step (5) is mixed in 180 DEG C of oil baths, heating mixing time is
30min；
(7) it after step (6) products therefrom is dry, grinding is crushed, is placed in sintering furnace and is heat-treated, 600 DEG C of constant temperature
Rich lithium manganese anode material 8h modified to get the micro- acidification in surface as shown in Figure 3 and compound coating.
Compared with basis material, 2 product photo grain corner of the embodiment of the present invention is rounder and more smooth, and between particle gap by glass
State composite oxides are filled, and complete clad is formed, and are conducive to the improvement of material circulation performance.
Embodiment 3:
A kind of rich lithium manganese anode material that the micro- acidification in surface and compound coating of the invention as shown in Figure 4 are modified, packet
Include the composite oxides of rich lithium manganese positive electrode active materials matrix and matrix outer cladding；The glassy state composite oxides be Li, B and
The composite oxides of Zr, the molecular formula of rich lithium manganese positive electrode active materials is represented by 0.5Li in the present embodiment2MnO3·
0.5LiNi0.5Mn0.5O2.Li in composite oxides derives from the remnants of the matrix surface of rich lithium manganese positive electrode active materials
Li2CO3, LiOH and free state lithium ion.In the present embodiment, B element content accounts for entire rich lithium manganese in glassy state composite oxides
The 0.1wt% of positive electrode, metal Zr account for the 0.08% of entire rich lithium manganese anode material.
The preparation method for the rich lithium manganese anode material that the micro- acidification in the above-mentioned surface of the present embodiment and compound coating are modified,
Specifically includes the following steps:
(1) 0.5Li that 1000g is uncoated2MnO3·0.5LiNi0.5Mn0.5O2Rich lithium manganese positive electrode active materials matrix, adds
Enter in 3L deionized water, is stirred 5min.Then 50ml/min rate is slowly filled with CO2, 10min is mixed；
(2) 3.765g zirconium nitrate is dissolved in 150mL deionized water, is mixed evenly, obtain metal salt solution；
(3) 3.220g boron oxide is dissolved in 150mL deionized water, is mixed evenly, obtain boric acid solution；
(4) metal salt solution and boric acid solution of above-mentioned preparation are slowly added in step (1) resulting mixed solution,
Accelerate stirring 5min, is mixed evenly；
(5) it being slowly dropped into ammonium hydroxide in step (4) resulting mixed solution, pH value of solution to be mixed is stablized at 7.0~8.0,
20min is mixed；By gained mixture, heating stirring obtains mixture when mixture loses flowability under the conditions of 80 DEG C
Colloidal sol；
(6) the resulting mixture colloidal sol of step (5) is mixed in 180 DEG C of oil baths, heating mixing time is
30min；
(7) it after step (6) products therefrom is dry, grinding is crushed, is placed in sintering furnace and is heat-treated, 650 DEG C of constant temperature
Rich lithium manganese anode material 8h modified to get the micro- acidification in surface as shown in Figure 4 and compound coating.
Compared with basis material, 3 product photo grain corner of the embodiment of the present invention is rounder and more smooth, and between particle gap by glass
State composite oxides are filled, and complete clad is formed, and are conducive to the improvement of material circulation performance.
Comparative example 1: the preparation of dry method coating modification richness lithium manganese anode material
(1) 4.576g boric acid, 1.134g nano aluminium oxide and 1000g richness lithium manganese anode material are added in 5L ball grinder,
And alumina balls are added and carry out ball milling mixing, wherein ball material mass ratio is 1:1,50rpm mixing 3h；
(2) by step (1) mixture, it is modified to get lithium, boron, aluminium compound coating that constant temperature 8h at 600 DEG C is placed in Muffle furnace
Rich positive pole of lithium manganese battery material.
Comparative example 2: the preparation of the modified rich lithium manganese anode material of wet process package
(1) 8.342g ANN aluminium nitrate nonahydrate is dissolved in 300mL deionized water, stirs to obtain aluminum nitrate solution；
(2) ammonium hydroxide is added in step (1) resulting solution, until pH7.0~7.5, obtains that particle is tiny and uniform glue
Liquid solution；
(3) 4.576g boric acid is added in the colloidal solution obtained by step (2), is dispersed with stirring uniformly；
(4) 1000g richness lithium manganese anode material matrix is added in step (3) resulting colloidal solution, accelerates to be stirred
0.5h；
(5) mixture obtained by step (4) is placed in 120 DEG C of air dry oven dry 8h；
(6) by after the grinding of dried object obtained by step (5), be placed in sintering furnace and be heat-treated, 600 DEG C of constant temperature 8h to get
The rich lithium manganese anode material of wet process coating modification.
Comparative example 3: the preparation of dry method coating modification richness lithium manganese anode material
(1) 5L ball grinder is added in 3.220g boron oxide, 1.081g nano zircite and 1000g richness lithium manganese anode material
In, and alumina balls are added and carry out ball milling mixing, wherein ball material mass ratio is 1:1,50rpm mixing 3h；
(2) by step (1) mixture, it is modified to get lithium, boron, aluminium compound coating that constant temperature 8h at 650 DEG C is placed in Muffle furnace
Rich positive pole of lithium manganese battery material.
It with conductive black, binder PVDF is in mass ratio respectively 84:8:8's by the positive electrode prepared by above-mentioned steps
Ratio is made solvent with NMP and is applied on Al foil after mixing, after 120 DEG C of dry 12h, rolls and is punched into 12mm disk, in argon
MIKROUNA Super (1220/750) glove box (O of gas shielded2< 1ppm, H2O < 1ppm) in, cathode assembling is made with lithium piece
At CR2032 type button cell, electrochemical property test is carried out under 2.0~4.6V voltage range.Test result is as follows 1 institute of table
Show.
Table 1: the button cell chemical property knot of gained positive electrode assembling in embodiment 1,2,3 and comparative example 1,2,3
Fruit
It can be seen that from above-mentioned test data
1) there is obvious shortcoming in traditional method for coating, although product cyclical stability, material discharging can be promoted effectively
Capacity and multiplying power are significantly affected, and product first charge discharge efficiency also decreases；
2) compared with the modified rich lithium manganese anode material of tradition, using the appearance for the first time of rich lithium manganese anode material prepared by the present invention
Amount is respectively 226.5mAh/g, 227.3mAh/g, 226.1mAh/g, and it is very small to be influenced loss capacity by cladding；First charge-discharge
Efficiency is respectively 87.6%, 87.8%, 87.0%, and efficiency is obviously improved；1C/0.2C be respectively 85.2%, 85.5%,
84.3%, high rate performance is slightly promoted；50 weeks capacity retention ratios are respectively 98.3%, 98.6%, 99.0%, and cycle performance is obvious
Improve.
Therefore the micro- acidification in surface of the present invention and the modified rich lithium manganese anode material electrical property of compound coating obtain
It is obviously improved.It can be effectively improved using the modified rich lithium manganese material of the micro- acidification in surface prepared by the present invention and compound coating
The performances such as circulation, the multiplying power of battery further increase cyclical stability and safety of lithium ion battery etc., for rich lithium manganese anode
Material is preferably applied for lithium ion battery and creates advantage.
Claims (10)
1. a kind of modified rich lithium manganese anode material of compound coating, which is characterized in that the richness lithium manganese anode material includes rich lithium
The composite oxides of manganese positive electrode active materials matrix and matrix outer cladding；The composite oxides are answering for Li, B and metal Me
Oxide is closed, and the metal Me is one or more of Al, Ti, Zr, Mg, W.
2. the modified rich lithium manganese anode material of compound coating according to claim 1, which is characterized in that the richness lithium manganese is just
The molecular formula of pole active material is expressed as xLi2MnO3·(1-x)LiMO2, wherein M is at least one in Ni, Co, Mn, Fe, Cr
Kind, 0.1≤x≤0.9.
3. the modified rich lithium manganese anode material of compound coating according to claim 1, which is characterized in that the combined oxidation
Li in object derives from the remaining Li of the matrix surface of the rich lithium manganese positive electrode active materials2CO3, LiOH and free state lithium from
Son.
4. the modified rich lithium manganese anode material of compound coating according to any one of claim 1-3, which is characterized in that institute
0.01wt%~1wt% that B element content in composite oxides accounts for entire rich lithium manganese anode material is stated, metal Me accounts for entire rich lithium
The 0.05%~0.3% of manganese anode material.
5. the modified rich lithium manganese anode material of compound coating according to any one of claim 1-3, which is characterized in that institute
The capacity for the first time for stating rich lithium manganese anode material is respectively 226.0mAh/g or more, 86.8% or more first charge-discharge efficiency.
6. a kind of preparation method of the modified rich lithium manganese anode material of compound coating, which comprises the following steps:
(1) rich lithium manganese positive electrode active materials matrix is added in deionized water according to mass ratio 1:2~1:5, is mixed；And
CO is slowly filled in mixed liquor2Gas；
(2) soluble metallic salt of metal Me is dissolved in solvent, stirs evenly to obtain solution A；
(3) boron compound is dissolved in solvent, stirs evenly to obtain solution B；
(4) solution A, B is added into above-mentioned steps (1) resulting mixed liquor, be uniformly mixed, make metal Me ion, Li from
Son and boracic uniform ion are scattered in mixed solution；
(5) ammonium hydroxide is gradually instilled obtained by the above-mentioned steps (4) in mixed solution, adjusting is in neutrality mixed solution or alkalescent,
The mixed solution is heated under the conditions of 60 DEG C~80 DEG C simultaneously, until solution loses flowability, obtains colloidal mixture；
(6) colloidal mixture for obtaining above-mentioned steps (5) is mixed under the conditions of 160 DEG C~220 DEG C, is melting it
The material surface of described matrix is uniformly wrapped under state；
(7) above-mentioned steps (6) products therefrom is dry, grinding, then constant temperature is heat-treated 4~10h at 300 DEG C~700 DEG C, obtains
The rich lithium manganese anode material modified to the micro- acidification in surface and compound coating.
7. preparation method according to claim 6, it is characterised in that: the solvent is one of water, ethyl alcohol；The step
Suddenly in (2), soluble metallic salt and solvent are to be configured to solution A by the mass ratio of 1:10~1:50.
8. preparation method according to claim 6 or 7, it is characterised in that: in the step (1), every liter of mixed liquor CO2Gas
It is 10~100ml/min that body, which is filled with speed, and inflation incorporation time is 1~15min.
9. preparation method according to claim 6 or 7, it is characterised in that: in the step (3), the boron compound is
At least one of boron oxide and boric acid, the boron compound and solvent are to be configured to solution B by the mass ratio of 1:10~1:50.
10. preparation method according to claim 6 or 7, it is characterised in that: in the step (4), the time of mixing
Control is in 1~10min；In the step (5), (6), the time of mixing is controlled in 10~60min.
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