CN101777647B - Lithium ion battery surface clad anode material and preparation method thereof - Google Patents
Lithium ion battery surface clad anode material and preparation method thereof Download PDFInfo
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- CN101777647B CN101777647B CN2010101191722A CN201010119172A CN101777647B CN 101777647 B CN101777647 B CN 101777647B CN 2010101191722 A CN2010101191722 A CN 2010101191722A CN 201010119172 A CN201010119172 A CN 201010119172A CN 101777647 B CN101777647 B CN 101777647B
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Abstract
The invention discloses a method for preparing a lithium ion battery surface clad anode material, which comprises the following steps of: (1) adding one or more salt compounds containing clad metal M into a solvent A for hydrolysis to obtain a hydrolysate; (2) throwing a lithium-containing anode active material into the hydrolysate, fully stirring the mixture, regulating pH value, and making a hydrolysis product M(OH)2n deposited and uniformly adsorbed on the surface of the lithium-containing anode active material; (3) drying the lithium-containing anode active material adsorbed with the hydrolysis product M(OH)2n; and (4) roasting the dried lithium-containing anode active material of which the surface is adsorbed with the hydrolysis product M(OH)2n to form the anode active material clad by a metallic oxide MOn. The lithium ion battery surface clad anode material prepared by the method can obviously improve the energy density, safety performance and charge-discharge cycle stability of a lithium ion battery. In addition, the invention also discloses the lithium ion battery surface clad anode material prepared by the method and the lithium ion battery using the material.
Description
Technical field
The present invention relates to a kind of lithium ion battery, especially a kind of lithium ion battery surface clad anode material and preparation method thereof.
Background technology
Along with the miniaturization day by day of mobile devices such as mobile phone, digital camera, notebook computer and portable DVD player and lightening, market also improves constantly the requirement of energy density, security performance and the cycle life of lithium ion battery.
Lithium ion battery generally comprises: positive plate, negative plate, be interval in the barrier film between the positive/negative plate; And electrolyte; Wherein, Positive plate comprises plus plate current-collecting body and is distributed in the positive electrode active materials on the plus plate current-collecting body that negative plate comprises negative current collector and is distributed in the negative active core-shell material on the negative current collector.At present, the positive electrode active materials of lithium ion battery commonly used has layer structure LiCoO
2And LiNiO
2, spinel structure LiMn
2O
4, and LiNiCoMnO
2Deng multicomponent material.
But above-mentioned positive electrode active materials all has shortcoming separately: LiCoO
2Charging voltage can not surpass 4.2V, LiNiO
2Structural instability, LiMn
2O
4High-temperature behavior bad, LiNiCoMnO
2Voltage platform low; Therefore need carry out modification to these positive electrode active materials handles; It is the most effective one of modification processing method that positive electrode active materials is carried out that the surface coat to handle: with the surface of a spot of oxidate at positive electrode active materials; Can under the prerequisite of loss material specific capacity not, effectively improve the structural stability of positive electrode active materials; Stop positive electrode active materials and electrolyte generation side reaction, therefore can improve energy density, security performance and the charge and discharge cycles stability of lithium ion battery.
Disclosed the modification processing method of multiple positive electrode active materials in the prior art; Like the U.S. Pat of announcing on November 4th, 2,008 7; 445; 871 have just disclosed: prepare clad material through liquid phase method, then with dried clad material and positive electrode active materials mixed sintering, coat processing positive electrode active materials is carried out the surface.But during according to the method for preparing surface clad anode material, clad material can not be coated on the surface of positive electrode active materials equably, has influenced energy density, security performance and the charge and discharge cycles stability of lithium ion battery.
In view of this, necessary a kind of lithium ion battery surface clad anode material and preparation method thereof that provides with ideal capacity density, security performance and charge and discharge cycles stability.
Summary of the invention
The objective of the invention is to: a kind of lithium ion battery surface clad anode material with ideal capacity density, security performance and charge and discharge cycles stability and preparation method thereof is provided.
In order to realize the foregoing invention purpose, the invention provides a kind of preparation method of lithium ion battery surface clad anode material, it may further comprise the steps:
(1) one or more salt compounds that contain clad metal M are joined carries out 0～100 ℃ of hydrolysis 0.5～1 hour in the solvent orange 2 A, obtain hydrolyzate;
(2) will contain the lithium positive electrode active materials and put in the hydrolyzate that fully to stir and regulate the pH value be 5～11, make hydrolysate M (OH)
2nDeposition also evenly is adsorbed in the surface that contains the lithium positive electrode active materials, and adsorption time is 1～20 hour, wherein, when M is Ce, La, n=1.5; When M is Zr, n=2;
(3) will be adsorbed with hydrolysate M (OH)
2nContain the lithium positive electrode active materials 50～200 ℃ the oven dry 1～20 hour; And
(4) will dry the back surface adsorption hydrolysate M (OH) will be arranged
2nThe lithium positive electrode active materials that contains carry out roasting, form by metal oxide MO
nWhat coat contains the lithium positive electrode active materials, wherein, when M is Ce, La, n=1.5; When M is Zr, n=2.
The preparation method of lithium ion battery surface clad anode material of the present invention has made full use of the advantage of liquid phase method and solid phase method; The coated with uniform of the positive electrode active materials that makes according to the inventive method has a spot of oxide; The gram volume of surface clad anode material does not reduce, and uses specific discharge capacity, cycle performance and security performance under the lithium ion battery high voltage of the surface clad anode material that makes according to the inventive method all to be significantly increased.
As a kind of improvement of the preparation method of lithium ion battery surface clad anode material of the present invention, in the step (1), said solvent orange 2 A is a water.
As a kind of improvement of the preparation method of lithium ion battery surface clad anode material of the present invention, in the step (4), said roasting is carried out under 300-1300 ℃, and roasting time is 1-20 hour.
As a kind of improvement of the preparation method of lithium ion battery surface clad anode material of the present invention, before carrying out step (3) oven dry, with said solvent orange 2 A to being adsorbed with hydrolysate M (OH) in the step (2)
2nThe said lithium positive electrode active materials that contains wash.
As a kind of improvement of the preparation method of lithium ion battery surface clad anode material of the present invention, the said general formula that contains the lithium positive electrode active materials is LiCo
1-x-yM '
xM "
yO
2, in the formula, M ' and M " and be selected from a kind of among Al, Ce, Ga, Ge, La, Mg, Mn, Ni, Si, Sn, Ti, W, the Zn, 0≤x＜1,0≤y＜1, M ' and M respectively " inequality.
As a kind of improvement of the preparation method of lithium ion battery surface clad anode material of the present invention, in the step (4), said metal oxide MO
nIn M be selected among Ce, La, the Zr one or more, wherein, when M is Ce, La, n=1.5; When M is Zr, n=2.
As a kind of improvement of the preparation method of lithium ion battery surface clad anode material of the present invention, the said salt compounds that contains clad metal M is water-soluble inorganic salts, alkoxide or acylate.
As a kind of improvement of the preparation method of lithium ion battery surface clad anode material of the present invention, the said salt compounds that contains clad metal M is K
2ZrF
6, La (NO
3)
36H
2O or Ce (NO
3)
36H
2O.
As a kind of improvement of the preparation method of lithium ion battery surface clad anode material of the present invention, the said weight that contains the salt compounds of clad metal M is the said 2%-32% that contains lithium positive electrode active materials weight.
In addition, the present invention also provides a kind of lithium ion battery surface clad anode material, and this lithium ion surface clad anode material makes according to preceding method.
In addition; The present invention also provides a kind of lithium ion battery, and it comprises positive plate, negative plate, is interval in the barrier film between the positive/negative plate, and electrolyte; Wherein, positive plate evenly is mixed and made into by lithium ion battery surface clad anode material and conductive carbon powder, the binding agent that preceding method makes.
Description of drawings
Below in conjunction with accompanying drawing and embodiment, lithium ion battery surface clad anode material of the present invention and preparation method thereof is elaborated, wherein:
Fig. 1: A1, B1 are respectively LiCoO
2Coat ZrO
2The SEM figure (amplifying 3000 times) of front and back, A2, B2 are respectively LiCoO
2Coat ZrO
2The SEM figure (amplifying 30000 times) of front and back.
Fig. 2: LiCoO
2Coat ZrO
2Front and back are being in the half-cell of negative pole with the lithium metal, in the 3.0-4.5V scope, and the specific discharge capacity-cycle graph under the 0.2C, wherein, A is for after coating, and B is for before coating.
Fig. 3: LiCoO
2Before and after the clading ZnO, be in the half-cell of negative pole with the lithium metal, in the 3.0-4.5V scope, the specific discharge capacity-cycle graph under the 0.2C, wherein, A is for after coating, and B is for before coating.
Fig. 4: LiNi
0.8Co
0.2O
2Coat TiO
2Front and back are being in the half-cell of negative pole with the lithium metal, in the 3.0-4.3V scope, and the specific discharge capacity-cycle graph under the 0.2C, wherein, A is for after coating, and B is for before coating.
Fig. 5: LiNi
0.8Co
0.2O
2Coat SnO
2Front and back are being in the half-cell of negative pole with the lithium metal, in the 3.0-4.3V scope, and the specific discharge capacity-cycle graph under the 0.2C, wherein, A is for after coating, and B is for before coating.
Fig. 6: LiNi
1/3Co
1/3Mn
1/3O
2Coated Si O
2Front and back are being in the half-cell of negative pole with the lithium metal, in the 3.0-4.5V scope, and the specific discharge capacity-cycle graph under the 0.2C, wherein, A is for after coating, and B is for before coating.
Fig. 7: LiNi
0.5Co
0.2Mn
0.3O
2Coating before and after the MgO, is being in the half-cell of negative pole with the lithium metal, in the 3.0-4.5V scope, and the specific discharge capacity-cycle graph under the 0.2C, wherein, A is for after coating, and B is for before coating.
Fig. 8: LiNi
0.8Co
0.2O
2Coat LaO
1.5Front and back are being in the half-cell of negative pole with the lithium metal, in the 3.0-4.3V scope, and the specific discharge capacity-cycle graph under the 0.2C, wherein, A is for after coating, and B is for before coating.
Fig. 9: LiNi
0.8Co
0.2O
2Coat CeO
1.5Front and back are being in the half-cell of negative pole with the lithium metal, in the 3.0-4.3V scope, and the specific discharge capacity-cycle graph under the 0.2C, wherein, A is for after coating, and B is for before coating.
Figure 10: LiCoO
2Coat AlO
1.5Front and back are being in the half-cell of negative pole with the lithium metal, in the 3.0-4.5V scope, and the specific discharge capacity-cycle graph under the 0.2C, wherein, A is for after coating, and B is for before coating.
Figure 11: LiCoO
2Coat AlZrO
nFront and back are being in the half-cell of negative pole with the lithium metal, in the 3.0-4.5V scope, and the specific discharge capacity-cycle graph under the 0.2C, wherein, A is for after coating, and B is for before coating.
Figure 12: positive electrode active materials LiCoO
2Coat ZrO
2Front and back, in the full battery that with the Delanium is negative pole, in the 3.0-4.35V scope, the capability retention-cycle graph under the 0.2C, wherein, A is for after coating, and B is for before coating.
Embodiment
Below in conjunction with each embodiment, specify lithium ion battery surface clad anode material of the present invention and preparation method thereof.Wherein, if no special instructions, below covering amount among each embodiment all refer to: account for the percentage of total weight that the surface is coated with the positive electrode active materials of oxide by the weight of the oxide that salt compounds changed into that contains clad metal.
Instance 1:
Take by weighing 34.5g K
2ZrF
6Be dissolved in the 2kg deionized water, stir abundant hydrolysis at normal temperatures; Subsequently, under stirring condition, add 500g LiCoO
2, after stirring, the ammoniacal liquor of dropping 2M is adjusted to 7 with the pH value of mixture, continues to stir 5 hours; Then, stop stirring and filter, use deionized water wash, dry down at 85 ℃; At last, dried mixture 1000 ℃ of following roastings 2 hours, is slowly cooled to room temperature, obtain covering amount and be 3% surface clad anode material.
To evenly be mixed with into anode sizing agent with conductive carbon, Kynoar (PVDF) according to the surface clad anode material that preceding method makes; Be coated on and form positive pole on the plus plate current-collecting body; With the lithium sheet is negative pole, in glove box, forms button cell, carries out electro-chemical test.Fig. 1 is LiCoO
2Coat ZrO
2The SEM figure of front and back, the as can be seen from the figure represented ZrO of light-colored part
2Be coated on the represented LiCoO of dark part equably
2The surface.Fig. 2 is LiCoO
2Coat ZrO
2Front and back, in the 3.0-4.5V scope, the specific discharge capacity under the 0.2C-cycle graph contrast, the result shows, coats ZrO through the surface
2After positive electrode active materials LiCoO
2Gram volume performance promoted 5.5mAh/g.
Instance 2:
Take by weighing 55g Zn (NO
3)
26H
2O is dissolved in the 4kg deionized water, stirs at normal temperatures and makes its abundant hydrolysis; Subsequently, under stirring condition, add 500g LiCoO
2, after stirring, the ammoniacal liquor of dropping 2M is adjusted to 8 with the pH value of mixture, continues to stir 5 hours; Then, stop stirring and filter, use deionized water wash, dry down at 85 ℃; At last, dried mixture 600 ℃ of following roastings 2 hours, is slowly cooled to room temperature, obtain covering amount and be 3% surface clad anode material.
To evenly be mixed with into anode sizing agent with conductive carbon, PVDF according to the surface clad anode material that preceding method makes, and be coated on and form positive pole on the plus plate current-collecting body, be negative pole with the lithium sheet, in glove box, forms button cell, carries out electro-chemical test.Fig. 3 is LiCoO
2Before and after the clading ZnO, in the 3.0-4.5V scope, the specific discharge capacity under the 0.2C-cycle graph contrast, the result shows, through the positive electrode active materials LiCoO behind the surperficial clading ZnO
2Cycle performance be significantly improved.
Instance 3:
Take by weighing 36g metatitanic acid dimethyl ester and be dissolved in the 500g ethanol, stir at normal temperatures and make its abundant hydrolysis; Subsequently, under stirring condition, add 500g LiNi
0.8Co
0.2O
2, regulate pH to 11 and evenly stirred 5 hours; Then, stop stirring and filter, use washing with alcohol, dry down at 90 ℃; At last, dried mixture 500 ℃ of following roastings 5 hours, is slowly cooled to room temperature, obtain covering amount and be 3% surface clad anode material.
To evenly be mixed with into anode sizing agent with conductive carbon, PVDF according to the surface clad anode material that preceding method makes, and be coated on and form positive pole on the plus plate current-collecting body, be negative pole with the lithium sheet, in glove box, forms button cell, carries out electro-chemical test.Fig. 4 is LiNi
0.8Co
0.2O
2Coat TiO
2Front and back, in the 3.0-4.3V scope, the specific discharge capacity under the 0.2C-cycle graph contrast, the result shows, coats TiO through the surface
2After positive electrode active materials LiNi
0.8Co
0.2O
2Cycle performance obtained obvious improvement.
Instance 4:
Take by weighing 17.3g SnCl
4Be dissolved in the mixed solution of 500g deionized water and ethanol, the volume ratio of water and ethanol is 1: 9, stirs at normal temperatures; Subsequently, under stirring condition, add 500g LiNi
0.8Co
0.2O
2, after stirring, the ammoniacal liquor of dropping 2M is adjusted to 8 with the pH value of mixture, continues to stir 5 hours; Then, stop stirring and filtration, wash with aforementioned mixed solution, dry down at 85 ℃; At last, dried mixture 600 ℃ of following roastings 2 hours, is slowly cooled to room temperature, obtain covering amount and be 2% surface clad anode material.
The surface clad anode material that will make according to preceding method and conductive carbon, PVDF mix and are prepared into anode sizing agent, be coated on to form anodally on the plus plate current-collecting body, and be negative pole with the lithium sheet, in glove box, form button cell, carry out electro-chemical test.Fig. 5 is LiNi
0.8Co
0.2O
2Coat SnO
2Front and back, in the 3.0-4.3V scope, the specific discharge capacity under the 0.2C-cycle graph contrast, the result shows, coats SnO through the surface
2After positive electrode active materials LiNi
0.8Co
0.2O
2Cycle performance obtained obvious lifting.
Instance 5:
Take by weighing 52g Si (OC
2H
5)
4Be dissolved in the 1kg ethanol, stir at normal temperatures and make its abundant hydrolysis; Subsequently, under stirring condition, add 500g LiNi
1/3Co
1/3Mn
1/3O
2, regulate pH to 10, evenly stirred 5 hours; Then, stop stirring and filter, use washing with alcohol, dry down at 75 ℃; At last, dried mixture 500 ℃ of following roastings 5 hours, is slowly cooled to room temperature, obtain covering amount and be 3% surface clad anode material.
The surface clad anode material that will make according to preceding method and conductive carbon, PVDF mix and are prepared into anode sizing agent, be coated on to form anodally on the plus plate current-collecting body, and be negative pole with the lithium sheet, in glove box, form button cell, carry out electro-chemical test.Fig. 6 is LiNi
1/3Co
1/3Mn
1/3O
2Coated Si O
2Front and back, in the 3.0-4.5V scope, the specific discharge capacity under the 0.2C-cycle graph contrast, the result shows that after 20 circulations, the surface is coated with SiO
2Positive electrode active materials LiNi
1/3Co
1/3Mn
1/3O
2Specific capacity specific surface coated Si O not
2Positive electrode active materials LiNi
1/3Co
1/3Mn
1/3O
2Promoted 6.3mAh/g.
Instance 6:
Take by weighing 49g Mg (NO
3)
22H
2O is dissolved in the 2kg deionized water, stirs at normal temperatures and makes its abundant hydrolysis; Subsequently, under stirring condition, add 500g LiNi
0.5Co
0.2Mn
0.3O
2, after stirring, the ammoniacal liquor of dropping 2M is adjusted to 7 with the pH value of mixture, continues to stir 5 hours; Then, stop stirring and filter and use deionized water wash, dry down at 85 ℃; At last, dried mixture 600 ℃ of following roastings 2 hours, is slowly cooled to room temperature, obtain covering amount and be 3% surface clad anode material.
The surface clad anode material that will make according to preceding method and conductive carbon, PVDF mix and are prepared into anode sizing agent, be coated on to form anodally on the plus plate current-collecting body, and be negative pole with the lithium sheet, in glove box, form button cell, carry out electro-chemical test.Fig. 7 is LiNi
0.5Co
0.2Mn
0.3O
2Coat before and after the MgO, in the 3.0-4.5V scope, the specific discharge capacity under the 0.2C-cycle graph contrast, the result shows that the process surface coats the positive electrode active materials LiNi behind the MgO
0.5Co
0.2Mn
0.3O
2Gram volume performance promoted 2.5mAh/g.
Instance 7:
Take by weighing 10g La (NO
3)
36H
2O is dissolved in the mixed solution of 2kg deionized water and acetone, stirs; Subsequently, under stirring condition, add 500g LiNi
0.8Co
0.2O
2, after stirring, the ammoniacal liquor of dropping 2M is adjusted to 7 with the pH value of mixture, continues to stir 5 hours; Then, stop stirring and filtration, wash with aforementioned mixed solution, dry down at 85 ℃; At last, dried mixture 600 ℃ of following roastings 2 hours, is slowly cooled to room temperature, obtain covering amount and be 0.9% surface clad anode material.
The surface clad anode material that will make according to preceding method and conductive carbon, PVDF mix and are prepared into anode sizing agent, be coated on to form anodally on the plus plate current-collecting body, and be negative pole with the lithium sheet, in glove box, form button cell, carry out electro-chemical test.Fig. 8 is LiNi
0.8Co
0.2O
2Coat LaO
1.5Front and back, in the 3.0-4.3V scope, the specific discharge capacity under the 0.2C-cycle graph contrast, the result shows, coats LaO through the surface
1.5After positive electrode active materials LiNi
0.8Co
0.2O
2Cycle performance obtained obvious lifting.
Instance 8:
Take by weighing 13g Ce (NO
3)
36H
2O is dissolved in the mixed solution of 1kg deionized water and acetone, stirs; Subsequently, under stirring condition, add 500g LiNi
0.8Co
0.2O
2, after stirring, the ammoniacal liquor of dropping 2M is adjusted to 7 with the pH value of mixture, continues to stir 5 hours; Then, stop to stir and filtering, adopt the mixed solution washing of deionized water and acetone, dry down at 85 ℃; At last, dried mixture 600 ℃ of following roastings 2 hours, is slowly cooled to room temperature, obtain covering amount and be 1% surface clad anode material.
The surface clad anode material that will make according to preceding method and conductive carbon, PVDF mix and are prepared into anode sizing agent, be coated on to form anodally on the plus plate current-collecting body, and be negative pole with the lithium sheet, in glove box, form button cell, carry out electro-chemical test.Fig. 9 is LiNi
0.8Co
0.2O
2Coat CeO
1.5Front and back, in the 3.0-4.3V scope, the specific discharge capacity under the 0.2C-cycle graph contrast, the result shows, coats CeO through the surface
1.5After positive electrode active materials LiNi
0.8Co
0.2O
2Cycle performance obtained obvious lifting.
Instance 9:
Take by weighing 160g Al (CH
3COO)
3Be dissolved in the 0.5kg isopropyl alcohol, stir at normal temperatures and make its abundant hydrolysis; Subsequently, under stirring condition, add 500g LiCoO
2, regulate pH to 8, evenly stirred then 5 hours; Then, stop stirring and filter, adopt isopropyl alcohol to wash, dry down at 75 ℃; At last, dried mixture 500 ℃ of following roastings 5 hours, is slowly cooled to room temperature, obtain covering amount and be 8% surface clad anode material.
The surface clad anode material that will make according to preceding method and conductive carbon, PVDF mix and are prepared into anode sizing agent, be coated on to form anodally on the plus plate current-collecting body, and be negative pole with the lithium sheet, in glove box, form button cell, carry out electro-chemical test.Figure 10 is LiCoO
2Coat AlO
1.5Front and back, in the 3.0-4.5V scope, the specific discharge capacity under the 0.2C-cycle graph contrast, the result shows, coats AlO through the surface
1.5After positive electrode active materials LiCoO
2Gram volume performance promoted 3.3mAh/g.
Instance 10:
Take by weighing 10.5g ZrOCl
28H
2O is dissolved in the 100g water; Take by weighing 110.4g Al (NO
3)
39H
2O and being dissolved in fully in the 2kg deionized water, subsequently, under stirring condition at Al (NO
3)
3Add 500gLiCoO in the solution
2, after stirring, add aforementioned ZrOCl
2Solution, the ammoniacal liquor of Dropwise 5 M transfers to 5 with the pH value of mixture, continues to stir 5 hours; Then, stop stirring and filtration, washing, dry down at 85 ℃; At last, dried mixture 500 ℃ of following roastings 5 hours, is slowly cooled to room temperature, obtain covering amount and be 3.8% surface clad anode material.
The surface clad anode material that will make according to preceding method and conductive carbon, PVDF mix and are prepared into anode sizing agent, be coated on to form anodally on the plus plate current-collecting body, and be negative pole with the lithium sheet, in glove box, form button cell, carry out electro-chemical test.Figure 11 is LiCoO
2Coat AlZrO
nFront and back, in the 3.0-4.5V scope, the specific discharge capacity under the 0.2C-cycle graph contrast, the result shows that after 20 circulations, the surface is coated with AlZrO
nPositive electrode active materials LiCoO
2The specific capacity specific surface do not coat AlZrO
nPositive electrode active materials LiCoO
2Specific capacity promoted 5.3mAh/g.
Instance 11:
Coat ZrO according to previous embodiment 1 preparation surface
2Positive electrode active materials LiCoO
2And it is anodal with the surface clad anode material that makes and conductive carbon powder, the even mixing manufacture of binding agent; With the Delanium is negative pole; Positive plate, negative plate and barrier film are reeled with common process, make lithium ion battery through terminal welding, packaging foil encapsulation, fluid injection, the encapsulation moulding that changes into, bleeds then.Under 3.0-4.35V with coat before positive electrode active materials LiCoO
2Compare, the result is shown in figure 12.As can be seen from the figure, the surface coats ZrO
2After positive electrode active materials LiCoO
2After 200 circulations, its capacity keeps still can reaching 92%, and the surface does not coat ZrO
2Positive electrode active materials LiCoO
2After 200 circulations, capacity has dropped to 88%.Presentation of results: coat ZrO through the surface
2After, positive electrode active materials LiCoO
2Cycle performance under high voltage has obtained remarkable improvement.
According to the announcement and the instruction of above-mentioned specification, those skilled in the art in the invention can also change and revise above-mentioned execution mode.Therefore, the specific embodiment that discloses and describe above the present invention is not limited to also should fall in the protection domain of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this specification, these terms are explanation for ease just, the present invention is not constituted any restriction.
Claims (11)
1. the preparation method of a lithium ion battery surface clad anode material, it may further comprise the steps:
(1) one or more salt compounds that contain clad metal M are joined carries out 0～100 ℃ of hydrolysis 0.5～1 hour in the solvent orange 2 A, obtain hydrolyzate;
(2) will contain the lithium positive electrode active materials and put in the hydrolyzate that fully to stir and regulate the pH value be 5～11, make hydrolysate M (OH)
2nDeposition also evenly is adsorbed in the surface that contains the lithium positive electrode active materials, and adsorption time is 1～20 hour, wherein, when M is Ce, La, n=1.5; When M is Zr, n=2;
(3) will be adsorbed with hydrolysate M (OH)
2nContain the lithium positive electrode active materials 50～200 ℃ the oven dry 1～20 hour; And
(4) will dry the back surface adsorption hydrolysate M (OH) will be arranged
2nThe lithium positive electrode active materials that contains carry out roasting, form by metal oxide MO
nWhat coat contains the lithium positive electrode active materials, wherein, when M is Ce, La, n=1.5; When M is Zr, n=2.
2. the preparation method of lithium ion battery surface clad anode material according to claim 1, it is characterized in that: in the step (1), said solvent orange 2 A is a water.
3. the preparation method of lithium ion battery surface clad anode material according to claim 1, it is characterized in that: in the step (4), said roasting is carried out under 300-1300 ℃, and roasting time is 1-20 hour.
4. the preparation method of lithium ion battery surface clad anode material according to claim 1 is characterized in that: before carrying out step (3) oven dry, with said solvent orange 2 A to being adsorbed with hydrolysate M (OH) in the step (2)
2nThe said lithium positive electrode active materials that contains wash.
5. the preparation method of lithium ion battery surface clad anode material according to claim 1, it is characterized in that: the said general formula that contains the lithium positive electrode active materials is LiCo
1-x-yM '
xM "
yO
2, in the formula, M ' and M " and be selected from a kind of among Al, Ce, Ga, Ge, La, Mg, Mn, Ni, Si, Sn, Ti, W, the Zn, 0≤x＜1,0≤y＜1, M ' and M respectively " inequality.
6. the preparation method of lithium ion battery surface clad anode material according to claim 1 is characterized in that: said metal oxide MO
nIn M be selected among Ce, La, the Zr one or more, wherein, when M is Ce, La, n=1.5; When M is Zr, n=2.
7. the preparation method of lithium ion battery surface clad anode material according to claim 1, it is characterized in that: the said salt compounds that contains clad metal M is water-soluble inorganic salts, alkoxide or acylate.
8. the preparation method of lithium ion battery surface clad anode material according to claim 1, it is characterized in that: the said salt compounds that contains clad metal M is K
2ZrF
6, La (NO
3)
36H
2O or Ce (NO
3)
36H
2O.
9. the preparation method of lithium ion battery surface clad anode material according to claim 1, it is characterized in that: the said weight that contains the salt compounds of clad metal M is said 2% to 32% of the lithium positive electrode active materials weight that contains.
10. lithium ion battery surface clad anode material, it is characterized in that: said lithium ion battery surface clad anode material is to make according to each described method in the claim 1 to 9.
11. lithium ion battery; It comprises positive plate, negative plate, is interval in the barrier film between the positive/negative plate; And electrolyte, it is characterized in that: said positive plate evenly is mixed and made into by the described lithium ion battery surface clad anode material of claim 10 and conductive carbon powder, binding agent.
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| CN109524618B (en) | 2017-09-19 | 2020-09-18 | 宁德新能源科技有限公司 | Positive electrode material and lithium ion battery |
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| CN108390065A (en) * | 2018-01-25 | 2018-08-10 | 湖北师范大学 | A method of in li-ion electrode materials surface coating cerium oxide |
| CN111095619B (en) * | 2018-08-06 | 2022-08-12 | 中天新兴材料有限公司 | Preparation method of anode material, anode material and lithium ion battery |
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| CN112151781A (en) * | 2020-09-24 | 2020-12-29 | 贵州梅岭电源有限公司 | Rapid composite coating modification method for lithium battery positive electrode material |
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| CN101118962B (en) * | 2006-08-03 | 2010-05-12 | 比亚迪股份有限公司 | Method of lithium ion secondary battery anode active compound coating oxide layer |
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