CN100595947C - Production method for anode active material of lithium ion secondary battery - Google Patents
Production method for anode active material of lithium ion secondary battery Download PDFInfo
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- CN100595947C CN100595947C CN200610162114A CN200610162114A CN100595947C CN 100595947 C CN100595947 C CN 100595947C CN 200610162114 A CN200610162114 A CN 200610162114A CN 200610162114 A CN200610162114 A CN 200610162114A CN 100595947 C CN100595947 C CN 100595947C
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing an anode active material for a lithium ion secondary battery, wherein the method comprising the following steps of: contacting the anode active materialwith suspended liquid containing metallic oxides and/or silicon dioxide and a solution, wherein the metallic oxides contains metal(s) which can, together with a solvent, form the suspended liquid andcan be one or a plurality of metals in form of metallic dioxide from the groups II A, III A, IVA, I B, II B, III B, IV B, VI B, VII B of the periodic table of elements. The lithium ion secondary battery made by the method has good storage performance under high pressure environment and good recycling performance, with the anode active material of the battery having good stability under high potential.
Description
Technical field
The invention relates to a kind of preparation method of battery anode active material, more specifically say so about a kind of preparation method of anode active material of lithium ion secondary battery.
Background technology
In recent years,, adopt battery charge is used to higher current potential, therefore need to improve the utilance of positive active material in order to pursue the further high capacity of lithium rechargeable battery.But, when will be all the time charging to the voltage that is higher than more than the 4.2V as the lithium rechargeable battery of positive active material,, therefore can cause the cycle performance of battery relatively poor because this active agent stability reduces greatly with lithium cobalt oxygen.
In order to improve positive active material as the stability of lithium cobalt oxygen under high voltage, can be magnesium-doped in positive active material, metallic element such as titanium, zirconium.But reduce owing to metallic elements such as magnesium-doped, titanium, zirconium can cause the capacity of positive active material, under higher voltage, the stability of positive electrode active material lithium cobalt oxygen still can not satisfy the needs of practical application simultaneously.
The composite oxides that adopt nickel manganese cobalt are as battery positive electrode active material, though the stability of this positive active material under high potential is improved, but, under the charged state of high voltage, adopt the storge quality of battery under hot environment of this positive active material relatively poor.
CN1350706A discloses a kind of lithium mixed oxide particle of metal oxide-coated, applies a kind of metal oxide on this lithium mixed oxide particle, and described metal oxide is selected from ZnO, CaO, SrO, SiO
2, CaTiO
3, MgAl
2O
4, ZrO
2, Al
2O
3, Ce
2O
3, Y
2O
3, SnO
2, TiO
2With among the MgO one or more.This preparation method who is coated with the lithium mixed oxide particle of metal oxide comprises, with the positive active material particle suspending in organic solvent, this suspension is mixed with hydrolyzable solution of metal compound and hydrating solution, filter out coated particle then, dry also calcining, thus metal oxide is coated on around the positive active material.Adopt the stability of the positive active material that this method obtains stronger, the battery that is prepared by this positive active material also makes moderate progress at the storge quality under the hot environment, but the cycle performance of battery, and especially the cycle performance under high voltage is still relatively poor.
Summary of the invention
The cycle performance that the objective of the invention is to overcome the lithium rechargeable battery that positive electrode active materials that employing obtains by existing method prepares is poor, especially the shortcoming of the cycle performance difference of battery under high voltage, provide on a kind of basis that makes battery have good storge quality under hot environment and make battery anode active material having good stability under high potential, battery has the preparation method of the anode active material of lithium ion secondary battery of good circulation performance.
The present inventor finds, the existing method for preparing positive electrode active materials be with the positive active material impregnated with particles in the mixed solution of the solution of hydrolyzable metal and/or nonmetallic compound and hydrating solution, filter then, in order to make hydrolysate (metal hydroxides) be converted into metal oxide, also comprise the step of calcining at high temperature.Though adopt the method for high-temperature calcination can make metal and/or nonmetal hydroxide form oxide, and be coated on around the positive active material, metal and/or nonmetal oxide are not easy to come off, but, because after high-temperature calcination, form fine and close metal oxide layer on the surface of active material particle, when battery when carrying out first charge-discharge, electrolyte can't contact with the positive active material particle surface fully, therefore, electrolyte can't be fully and the positive electrode active material qualitative response, can not form the SEI film between electrolyte and positive active material.Carrying out along with the battery charging and discharging circulation, positive active material expands contraction, can cause breaking of oxide skin(coating), at this moment, electrolyte could contact and react the generation interfacial film fully with positive active material, continue reaction like this and can consume electrolyte rapidly, cause the circulation certain number of times after electrolyte be consumed totally, and the cycle performance of battery is worsened rapidly, in addition, electrolyte and positive electrode active material qualitative response can produce a large amount of gases when generating interfacial film, cause the cell expansion swell, exist safety because of suffering from.Especially in the high voltage charge and discharge process, more lithium ion is deviate from from positive active material, makes the activity of positive active material increase, and more violent with the reaction of electrolyte, the deterioration of the cycle performance of battery is just more obvious.
The invention provides a kind of preparation method of anode active material of lithium ion secondary battery, wherein, this method comprises positive active material is contacted with a kind of suspension, this suspension contains metal oxide and/or silicon dioxide and solvent, and the metal in the described metal oxide is selected from and can forms one or more in IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VB, VIB, the VIIB family metal oxide in the periodic table of elements of suspension with solvent.
Method of the present invention is directly battery positive electrode active material to be contacted with the suspension that contains metal oxide and/or silicon dioxide and solvent, described metal oxide and/or silica dioxide granule are adsorbed on the positive active material, and the step that there is no need to pass through high-temperature calcination can not make being coated on around the positive active material of described oxide compacting.Therefore, guaranteeing that battery has under the hot environment under the prerequisite of excellent storage performance, can also improve the stability of positive active material under high potential, and effectively improve the cycle performance of battery, make in the process of first charge-discharge, electrolyte can be penetrated into and be easy in the oxide skin(coating) contact with positive active material and react, in battery charge and discharge process subsequently, the a large amount of problems that consume of the electrolyte that also can not breaking of oxide skin(coating) occur and cause, make battery in charge and discharge process subsequently, have excellent cycle performance, therefore, improved the stable cycle performance of battery, especially under high voltage, cycle performance of battery has obtained tangible improvement especially.
Embodiment
According to method provided by the invention, wherein, this method comprises positive active material is contacted with a kind of suspension, this suspension contains metal oxide and/or silicon dioxide and solvent, and the metal in the described metal oxide is selected from and can forms one or more in IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VB, VIB, the VIIB family metal oxide in the periodic table of elements of suspension with solvent; Under the preferable case, described metal oxide is selected from one or more in magnesium oxide, alundum (Al, cuprous oxide, zinc oxide, yttria, titanium dioxide and the zirconia.
The consumption of described metal oxide and/or silicon dioxide makes the content of metal oxide in this positive electrode active materials and/or silicon dioxide be conventional content, generally, the weight ratio of described positive active material and metal oxide and/or silicon dioxide is 1: 0.001-0.02 is preferably 1: 0.003-0.01.If described positive active material contains multiple metal oxide, then the weight ratio of positive active material and described multiple metal oxide total weight is 1: 0.001-0.02 is preferably 1: 0.003-0.01.
According to the present invention, described suspension contains metal oxide and/or silicon dioxide and solvent, described solvent can be the aqueous solution of water, organic solvent or organic solvent, the various organic solvents of routine when described organic solvent can be selected from cell preparation are as in ethanol, N-N-methyl-2-2-pyrrolidone N-, oxolane, the methyl nitrosourea one or more.The weight ratio of described metal oxide and/or silicon dioxide and solvent is 0.0005-0.002: 1, be preferably 0.0005-0.0012: 1.
The preparation method of the described suspension that contains metal oxide and/or silicon dioxide can obtain after metal oxide and/or silicon dioxide and above-mentioned solvent are directly mixed, more even for what described metal oxide and/or silica dioxide granule were disperseed in solvent, to be more conducive to making described metal oxide and/or silicon dioxide be adsorbed on the positive active material equably, under the preferable case, after with metal oxide and/or silicon dioxide and solvent, adopt ultrasonic wave to disperse, and under vacuum condition, stir, to remove the bubble in the suspension.The method that described employing ultrasonic wave disperses and under vacuum condition, carry out the method for operation that stirring method is this area routine.The described time of disperseing with ultrasonic wave can be for greater than 1 minute, and the ultrasonic wave jitter time can not make the dispersion effect of yttria be further improved greater than after 30 minutes yet, and therefore, preferred jitter time is 10-20 minute; The described time of stirring under vacuum condition is not particularly limited, as long as can reach the purpose of removing bubble in the suspension.
The mode that positive active material is contacted with the suspension that contains metal oxide and/or silicon dioxide mixes positive active material and the suspension that contains metal oxide and/or silicon dioxide under agitation.
The median particle diameter D of described metal oxide and/or silicon dioxide
50Be the 0.01-0.5 micron, be preferably the 0.05-0.3 micron.
According to the present invention, this method also comprises the solid product after separating positive active material and suspension contacting, and dry this solid product.
Described separation positive active material and the method for solid product after suspension contacts can adopt the separation method of this area routine, as filtering or the method for centrifugation.
The method of described drying can adopt the drying means of this area routine, as air dry, forced air drying etc., described drying can be carried out under normal pressure, also can carry out under vacuum condition, under the preferable case, in order better to reach drying effect, make solvent more volatile, described drying is preferably carried out under vacuum condition, described vacuum condition comprises that vacuum degree is more than-0.8 MPa, is preferably-0.8 to-0.98 MPa.
The temperature of described drying is 90-180 ℃, is preferably 100-150 ℃, and for the intensive drying solid product, the time of described drying was at least 10 hours, was preferably 15-48 hour.
Positive active material of the present invention can be the positive active material of various routines in the lithium rechargeable battery, as, described positive active material can be selected from one or more in the lithium compound with following chemical general formula: Li
xNi
1-yCoO
2, in the formula, 0.9≤x≤1.1,0≤y≤1.0; Li
1+aM
bMn
2-bO
4, in the formula ,-0.1≤a≤0.2,0≤b≤1.0, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur; Li
mMn
2-nB
nO
2, in the formula, B is a transition metal, 0.9≤m≤1.1,0≤n≤1.0; Li
eNi
fMn
gCo
hO
2, in the formula, 0.5≤e≤1.1, f+g+h=1,0＜f≤0.5,0＜g≤0.5,0＜h≤0.5.
More obvious for the improvement that makes battery performance, the preferred positive active material that adopts is Li
eNi
fMn
gCo
hO
2Or Li
eNi
fMn
gCo
hO
2And Li
xCoO
2Mixture, described Li
eNi
fMn
gCo
hO
2And Li
xCoO
2Weight ratio be 9: 1-6: 4, and x=y=1 in the general formula.
The median particle diameter D of described positive active material
50Can be the 1-15 micron, be preferably the 5-12 micron.
Adopt in the active material for anode of Li-ion secondary battery of containing metal oxide that method of the present invention obtains and/or silicon dioxide, described oxide particle is not coated on around the positive active material fully, but be adsorbed on the positive active material, and there is certain clearance between the positive active material, thereby, on the one hand, in the process of the first charge-discharge of battery, electrolyte can be penetrated into and contact with positive active material in the metal oxide layer and react, improve battery capacity, and in battery charge and discharge process subsequently, the problem of a large amount of consumption of the electrolyte that also can not breaking of metal oxide layer occur and cause, on the other hand, under high voltage, when the positive active material that is adsorbed with oxide particle contacts with electrolyte, be adsorbed on oxide particle on the positive active material can restrain the active material surface should with violent the sending out of electrolyte, thereby reduced the risk of deterioration of battery, improved the stability that battery is worked under high voltage.Therefore the SC service ceiling voltage of lithium rechargeable battery of the present invention can reach 4.3-4.6V.
To be further described specifically the present invention by embodiment below.
Embodiment 1
The preparation of present embodiment explanation anode active material of lithium ion secondary battery.
With 5 gram median particle diameter D
50The yttria particle and 2500 ml waters that are 0.2 micron mix, and disperse 20 minutes with ultrasonic wave, stir 1 hour in de-airing mixer then, obtain containing the suspension of yttria.
Under agitation, with 500 gram median particle diameter D
50Be 8 microns positive active material LiNi
0.4Mn
0.3Co
0.3O
2(Japanese chemical company commodity) mix with the above-mentioned suspension that contains yttria, filter then, and at 120 ℃, vacuum degree obtained containing the positive active material of yttria in 15 hours for oven dry under-0.98 MPa, wherein, the content of yttria is 5 grams.
Embodiment 2
The preparation of present embodiment explanation anode active material of lithium ion secondary battery.
With 5 gram median particle diameter D
50Be 0.2 micron alundum (Al particle, 5 gram median particle diameter D
50The silica dioxide granule and 6000 ml waters that are 0.3 micron mix, and disperse 20 minutes with ultrasonic wave, stir 1 hour in de-airing mixer then, obtain containing the suspension of alundum (Al and silicon dioxide.
Under agitation, with 500 gram median particle diameter D
50Be 8 microns positive active material LiNi
0.4Mn
0.3Co
0.3O
2(Japanese chemical company commodity) mix with the above-mentioned suspension that contains alundum (Al particle and silica dioxide granule, filter then, and at 120 ℃, vacuum degree obtained containing the positive active material of alundum (Al and silicon dioxide in 20 hours for oven dry under-0.90 MPa, wherein, the content of alundum (Al is 5 grams, and the content of silicon dioxide is 5 grams.
Embodiment 3
The preparation of present embodiment explanation anode active material of lithium ion secondary battery.
With 1 gram median particle diameter D
50Be 0.1 micron titanium dioxide granule, 1.5 gram median particle diameter D
50The zirconia particles and 3200 ml waters that are 0.5 micron mix, and disperse 20 minutes with ultrasonic wave, stir 1 hour in de-airing mixer then, obtain containing titanium dioxide and zirconic suspension.
Under agitation, with 500 gram median particle diameter D
50Be 8 microns positive active material LiNi
0.4Mn
0.3Co
0.3O
2(Ningbo gold and company's commodity) contain titanium dioxide and zirconic suspension mixes with above-mentioned, filter then, and at 120 ℃, vacuum degree obtained containing titanium dioxide and zirconic positive active material in 48 hours for oven dry under-0.98 MPa, wherein, the content of titanium dioxide is 1 gram, and zirconic content is 1.5 grams.
Embodiment 4
The preparation of present embodiment explanation anode active material of lithium ion secondary battery.
With 0.5 gram median particle diameter D
50Yttria particle and 1000 milliliters of ethanol of being 0.2 micron mix, and disperse 20 minutes with ultrasonic wave, stir 1 hour in de-airing mixer then, obtain containing the suspension of yttria.
Under agitation, with 300 gram median particle diameter D
50Be 8 microns positive active material LiNi
0.4Mn
0.3Co
0.3O
2(Ningbo gold and company's commodity) and 200 gram positive active material LiCoO
2(FMC Corp.'s commodity) mix with the above-mentioned suspension that contains yttria, filter then, and at 120 ℃, vacuum degree obtained containing the positive active material of yttria in 48 hours for oven dry under-0.98 MPa, wherein, the content of yttria is 0.5 gram.
Embodiment 5
The preparation of present embodiment explanation anode active material of lithium ion secondary battery.
With 4 gram median particle diameter D
50Silica dioxide granule and 4000 milliliters of N-N-methyl-2-2-pyrrolidone N-s of being 0.2 micron mix, and disperse 20 minutes with ultrasonic wave, stir 1 hour in de-airing mixer then, obtain containing the suspension of silicon dioxide.
Under agitation, with 500 gram median particle diameter D
50Be 8 microns positive active material LiNi
0.4Mn
0.3Co
0.3O
2(Japanese chemical company commodity) mix with the above-mentioned suspension that contains silica dioxide granule, filter then, and at 120 ℃, vacuum degree obtained containing the positive active material of silicon dioxide in 20 hours for oven dry under-0.90 MPa, wherein, the content of silicon dioxide is 4 grams.
Comparative Examples 1
The preparation of this Comparative Examples explanation reference anode active material of lithium ion secondary battery.
(1) with 500 gram median particle diameter D
50Be 8 microns positive active material LiNi
0.4Mn
0.3Co
0.3O
2(Japanese chemical company commodity) mix with 2500 milliliters of ethanol, and water-bath is heated to 40 ℃.
(2) 30 gram acrylic acid yttrium acid esters salt are dissolved in 2500 milliliters of ethanol, mix and obtain coating solution, and in 6 hours, coating solution and 80 ml waters are slowly joined in the mixed solution of positive active material that above-mentioned steps (1) obtains and ethanol, described water is as hydrating solution, in order to ensure the carrying out of hydrolysis, in 15 hours, slowly add 200 ml waters again.
(3) filter the solution of above-mentioned steps (2), with product 100 ℃ dry 2 hours down, then 800 ℃ of calcinings 30 minutes down, obtain the reference active material for anode of Li-ion secondary battery of trioxygen-containingization two yttriums.The content of described yttria is about 1 weight % of positive active material.
Embodiment 6-10
This embodiment illustrates that positive electrode active materials obtained by the method for the present invention prepares lithium rechargeable battery
(1) Zheng Ji preparation
Earlier 3 gram adhesive polyvinylidene fluoride, 3 gram conductive agent acetylene blacks are joined among the 40 gram NMP, respectively 100 grams are prepared positive electrode active materials by embodiment 1-5 then and join in the said mixture, and in de-airing mixer, stir the uniform anode sizing agent of formation.
This slurry is coated on respectively on the aluminium foil equably, then in 150 ℃ of following oven dry, roll-in, cut to make and be of a size of 540 * 43.5 millimeters positive pole, wherein contain positive active material 5.8 grams respectively.
(2) preparation of negative pole
100 gram negative electrode active composition native graphites, 4 gram bonding agent polyvinylidene fluoride are joined among the 140 gram NMP, in de-airing mixer, stir then and form uniform cathode size.
This slurry is coated on the Copper Foil equably, then in 90 ℃ of following oven dry, roll-in, cut to make and be of a size of 500 * 44 millimeters negative pole, wherein contain 2.6 gram active component native graphites.
(3) assembling of battery
Above-mentioned positive and negative plate and polypropylene screen are wound into the pole piece of a square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in EC/DMC=1: form nonaqueous electrolytic solution in 1 the mixed solvent, this electrolyte is injected battery case with the amount of 3.8g/Ah, rectangular lithium ion battery A1-A5 is made in sealing respectively.
Comparative Examples 2
Method according to embodiment 6-10 prepares reference cell AC1, and different is the reference positive electrode active materials of used positive electrode active materials for being obtained by Comparative Examples 1.
Comparative Examples 3
Method according to embodiment 6-10 prepares reference cell AC2, and different is, used positive electrode active materials is the conventional positive active material LiNi of containing metal oxide and/or silicon dioxide not
0.4Mn
0.3Co
0.3O
2(Japanese chemical company commodity).
Embodiment 11-15
The lithium rechargeable battery that this embodiment explanation prepares the present invention carries out performance test
(1) anodal specific capacity test:
The lithium ion battery A1-A5 that will make by embodiment 6-10 respectively with the constant current charge of 900mA to 4.38V, after voltage rises to 4.38V,, be 25mA by electric current with constant-potential charge, shelved 10 minutes; With the constant current discharge of 900mA, be 3.0V then by voltage.Record the capacity of battery, and the specific capacity of counting cell positive pole according to the following equation.The result is as shown in table 1 below.
The weight of anode specific capacity (mAh/g)=battery capacity/positive electrode.
(2) cycle performance of battery test:
The lithium ion battery A1-A5 that makes by embodiment 6-10 respectively with the constant current of 900mA as continuous charge-discharge test, earlier with battery with the 900mAh current charges to by voltage 4.2V, with constant-potential charge, cut-off current is 25mA after voltage rises to 4.2V, shelves 10 minutes; Battery, was shelved 5 minutes to 3.0V with the 900mAh current discharge, repeated above-mentioned steps again, and different is that charging is respectively 4.38V by voltage, 4.48V and 4.58V.With the capacity of first charge-discharge as its initial capacity, record when the capacity of battery drop to its initial capacity 80% the time the cycle-index of process.The result is as shown in table 2 below.
(3) high-temperature storage performance test:
The battery of positive electrode capacity test will be finished, that is: will be according to after method be carried out first charge-discharge to the lithium ion battery A1-A5 that is made by embodiment 6-10 in (1), continuation recharges to 4.38V battery A1-A5 respectively with the electric current of 900mA, and the internal resistance of record battery.Battery placed 48 hours in 85 ℃ thermostat after, measure the internal resistance and the battery capacity of battery once more, and the capability retention of counting cell according to the following equation.
Battery capacity conservation rate %=stores the preceding battery capacity of back battery capacity/storage
The result is as shown in table 3 below.
Comparative Examples 4-5
The reference cell that this Comparative Examples explanation prepares Comparative Examples 2-3 carries out performance test
Method according to embodiment 11-15 is carried out performance test to battery, and different is that the battery of test is for to prepare reference cell AC1 and AC2 by Comparative Examples 2-3.Test result is respectively shown in table 1-3.
Table 1
| The embodiment numbering | The battery numbering | Anodal specific capacity (mAh/g) |
| Embodiment 11 | A1 | 157.7 |
| Embodiment 12 | A2 | 156.5 |
| Embodiment 13 | A3 | 156.2 |
| Embodiment 14 | A4 | 156.8 |
| Embodiment 15 | A5 | 156.9 |
| Comparative Examples 4 | AC1 | 150.0 |
| Comparative Examples 5 | AC2 | 157.9 |
Table 2
| The embodiment numbering | The battery numbering | 4.2V cycle-index | 4.38V cycle-index | 4.48V cycle-index | 4.58V cycle-index |
| Embodiment 11 | A1 | 468 | 426 | 413 | 382 |
| Embodiment 12 | A2 | 440 | 420 | 406 | 378 |
| Embodiment 13 | A3 | 439 | 415 | 403 | 377 |
| Embodiment 14 | A4 | 424 | 410 | 389 | 369 |
| Embodiment 15 | A5 | 448 | 416 | 403 | 379 |
| Comparative Examples 4 | AC1 | 369 | 328 | 296 | 208 |
| Comparative Examples 5 | AC2 | 413 | 367 | 219 | 139 |
Table 3
Data from table 1 as can be seen, though contain metal oxide and/or silicon dioxide in the positive active material of the present invention's preparation, make the corresponding minimizing of the ratio of positive active material in the cell positive material, but the reference cell that does not contain the positive active material preparation of metal oxide and/or silicon dioxide with the usefulness of Comparative Examples 3 is compared, and the positive electrode capacity of battery does not obviously change.
Data from table 2 as can be seen, the cycle performance of the battery that the positive electrode active materials that obtains in employing method of the present invention prepares is good, particularly under the high voltage (4.3V-4.6V), when the capacity of battery drop to its initial capacity 80% the time the cycle-index of process apparently higher than the cycle-index of reference cell, illustrate that the cycle performance of battery of the present invention is significantly improved.
Data from table 3 as can be seen, the capability retention of battery of the present invention after high-temperature storage is higher, illustrates that the high-temperature stability of battery anode active material is good, therefore, the stable performance of battery under hot environment; In addition, the internal resistance of cell was also lower after high temperature was preserved.
Above presentation of results, the lithium rechargeable battery that the positive electrode active materials that adopts method of the present invention to obtain prepares have high power capacity, good high-temperature storage performance and excellent cycle performance simultaneously.
Claims (8)
1, a kind of preparation method of anode active material of lithium ion secondary battery is characterized in that, this method is made up of following step:
(1) positive active material is contacted with a kind of suspension;
(2) solid product after separating positive active material and suspension contact, and this solid product of drying, the temperature of drying is 90-180 ℃;
Described suspension contains metal oxide and/or silicon dioxide and solvent, described positive electrode active materials comprises positive active material and is adsorbed on metal oxide and/or silicon dioxide on the positive active material, and the metal in the described metal oxide is selected from and can forms one or more in IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VB, VIB, the VIIB family metal oxide in the periodic table of elements of suspension with solvent; The median particle diameter D of described metal oxide and/or silicon dioxide
50Be the 0.01-0.5 micron.
2, method according to claim 1, wherein, the weight ratio of described positive active material and metal oxide and/or silicon dioxide is 1: 0.001-0.02.
3, method according to claim 1, wherein, the weight ratio of described metal oxide and/or silicon dioxide and solvent is 0.0005-0.002: 1.
4, according to claim 1 or 3 described methods, wherein, described solvent is the aqueous solution of water, organic solvent or organic solvent; Described organic solvent is selected from one or more in ethanol, N-N-methyl-2-2-pyrrolidone N-, oxolane and the methyl nitrosourea.
5, method according to claim 1, wherein, the described mode that positive active material is contacted with the suspension that contains metal oxide and/or silicon dioxide mixes positive active material and the suspension that contains metal oxide and/or silicon dioxide under agitation.
6, according to claim 1,2,3 or 5 described methods, wherein, described metal oxide is selected from one or more in magnesium oxide, alundum (Al, cuprous oxide, zinc oxide, yttria, titanium dioxide and the zirconia.
7, according to claim 1,2 or 5 described methods, wherein, described positive active material is selected from one or more in the lithium compound with following chemical general formula:
A) Li
xNi
1-yCoO
2, in the formula, 0.9≤x≤1.1,0≤y≤1.0;
B) Li
1+aM
bMn
2-bO
4, in the formula ,-0.1≤a≤0.2,0≤b≤1.0, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur;
C) Li
mMn
2-nB
nO
2, in the formula, B is a transition metal, 0.9≤m≤1.1,0≤n≤1.0; With
D) Li
eNi
fMn
gCo
hO
2, in the formula, 0.5≤e≤1.1, f+g+h=1,0＜f≤0.5,0＜g≤0.5,0＜h≤0.5.
8, method according to claim 7, wherein, described positive active material is D), or D) and weight ratio A) be 9: 4 A) and mixture D), and x=y=1 in the general formula 1-6:.
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| WO2010079963A2 (en) * | 2009-01-06 | 2010-07-15 | 주식회사 엘지화학 | Positive electrode active material and lithium secondary battery comprising the same |
| CN102800868A (en) * | 2012-08-30 | 2012-11-28 | 中国科学技术大学 | Composition of positive electrode material of lithium-ion battery and lithium-ion battery |
| CN103972486B (en) * | 2014-05-07 | 2016-05-25 | 青岛新正锂业有限公司 | A kind of surface modifying method of anode material for lithium-ion batteries |
| CN109671915A (en) * | 2017-10-13 | 2019-04-23 | 中国科学院物理研究所 | A kind of method and its application reducing secondary battery positive electrode material pH value |
| CN109585847B (en) * | 2018-12-03 | 2020-06-19 | 重庆工程职业技术学院 | Quick-charging lithium titanate battery and preparation method thereof |
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