CN102347470B - Cobalt acid lithium composite material granule and preparation method thereof, and lithium ion battery - Google Patents
Cobalt acid lithium composite material granule and preparation method thereof, and lithium ion battery Download PDFInfo
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Abstract
The present invention relates to a kind of cobalt acid lithium composite material granule, it includes positive active material granule and is coated on the phosphoric acid aluminium lamination of this positive active material particle surface, and this positive active material granule is cobalt acid lithium or cation doping acid lithium granule.The invention still further relates to the preparation method of a kind of anode composite material of lithium ion battery granule, comprising: provide aluminum nitrate solution；Adding in this aluminum nitrate solution by positive active material granule to be covered, this positive active material granule is cobalt acid lithium or cation doping acid lithium granule, controls the addition of this positive active material, forms a mixture；Phosphate solution adds this mixture react, form phosphoric acid aluminium lamination at this positive active material particle surface；And this surface of heat treatment has the positive active material granule of phosphoric acid aluminium lamination, obtain anode composite material granule.The invention still further relates to a kind of lithium ion battery.
Description
Technical field
The present invention relates to a kind of cobalt acid lithium composite material granule and preparation method thereof, and lithium ion battery,
Particularly relate to a kind of cobalt acid lithium composite material granule being compounded to form with aluminum phosphate and preparation method thereof, and
Lithium ion battery.
Background technology
Use other material to form cladding the particle surface of active substance of lithium ion battery anode, be existing
The common method in technology, positive active material being modified.Such as, at the particle surface of LiFePO4
It is coated with one layer of carbon and can effectively solve the problem that LiFePO4 electric conductivity is relatively low, make to be coated with the phosphoric acid of carbon-coating
Ferrum lithium has preferable electric conductivity.It addition, prior art is it has been shown that at cobalt acid lithium or other positive-active
Material grains Surface coating aluminum phosphate can improve the heat stability of lithium ion cell positive and (refer to document
“Correlation between AlPO4nanoparticle coating thickness on LiCoO2cathode
And thermal stablility " J.Cho, Electrochimica Acta 48 (2003) 2807-2811 and patent
Number it is the United States Patent (USP) of 7,326,498).
Prior art is first to prepare aluminum phosphate granule to divide by the method for aluminum phosphate clad anode active substance
Dissipate the dispersion liquid formed in water, and positive active material granule is added this aluminum phosphate prepared
In the dispersion liquid of grain, make aluminum phosphate granular absorption at positive active material bulky grain table by the effect of absorption
Face, then the water in dispersion liquid is evaporated, and heat treatment at 700 DEG C, form surface and there is aluminum phosphate
The positive active material of grain.
But, owing to aluminum phosphate is water insoluble, aluminum phosphate granule is likely to be formed reunion when disperseing in water,
And when a large amount of positive active materials are added in aluminum phosphate dispersion liquid, the positive active material being initially charged
Adsorbing a large amount of aluminum phosphate granule, the rear positive active material granule added then may adsorb less than enough phosphorus
Acid alumina particles.Referring to Fig. 8, even if can be good at cladding, said method determines that this product 20 is from micro-
See in sight be the aluminum phosphate fractions distribution with little granule 22 on positive active material bulky grain 24 surface, and
Non-one layer of uniform aluminum phosphate material layer.Therefore, formed on positive active material surface by said method
Aluminum phosphate clad is the most uniform, it is impossible to ensure that each positive active material surface all can be coated with uniformly
One layer of aluminum phosphate, so that applying the cycle performance of lithium ion battery of this positive active material bad, makes this
Method is difficult to heavy industrialization application.
Summary of the invention
In view of this, necessary offer one can form uniform aluminum phosphate bag at cobalt acid lithium particle surface
The method of coating, and there is the cobalt acid lithium composite material granule of this aluminum phosphate clad, and apply this cobalt
The lithium ion battery of acid lithium composite material granule.
A kind of cobalt acid lithium composite material granule, it includes positive active material granule and is coated on the work of this positive pole
The phosphoric acid aluminium lamination on property material grains surface, this positive active material granule is cobalt acid lithium or cation doping acid lithium
Grain.
The preparation method of a kind of anode composite material of lithium ion battery granule, comprising: provide aluminum nitrate molten
Liquid；Positive active material granule to be covered is added in this aluminum nitrate solution, this positive active material
Grain is cobalt acid lithium or cation doping acid lithium granule, controls the addition of this positive active material, forms a mud
Shape mixture；Phosphate solution adds this muddy mixture react, at this positive active material
Particle surface forms phosphoric acid aluminium lamination；And this surface of heat treatment has the positive active material of phosphoric acid aluminium lamination
Grain, obtains anode composite material granule.
A kind of lithium ion battery, including positive pole, this positive pole includes cobalt acid lithium composite material granule, this cobalt acid
Lithium composite material granule includes positive active material granule and is coated on this positive active material particle surface
Phosphoric acid aluminium lamination, this positive active material granule is cobalt acid lithium or cation doping acid lithium granule.
Compared to prior art, present invention, avoiding the absorption produced due to solid mixing uneven, cause
The phenomenon that aluminum phosphate cladding is uneven, is suitable for heavy industrialization application.It addition, the present invention can live at positive pole
Property material grains Surface Creation a layer thickness uniformly and continuous print phosphoric acid aluminium lamination, rather than by aluminum phosphate granulation mass
Amass at positive active material particle surface, therefore there is more preferable chemical property.
Accompanying drawing explanation
Fig. 1 is the structural representation of embodiment of the present invention aluminum phosphate clad anode active substance.
Fig. 2 is the stereoscan photograph of embodiment of the present invention aluminum phosphate cladding cobalt acid lithium.
Fig. 3 is the transmission electron microscope photo of embodiment of the present invention aluminum phosphate cladding cobalt acid lithium.
Fig. 4 is the stereoscan photograph of the aluminum phosphate cladding cobalt acid lithium of the magnification at high multiple of contrast experiment.
Fig. 5 is the stereoscan photograph of the aluminum phosphate cladding cobalt acid lithium of the low power amplification of contrast experiment.
Fig. 6 is the cycle performance test curve of the positive active material of embodiment of the present invention aluminum phosphate cladding.
Fig. 7 is the cycle performance test curve of the positive active material of the aluminum phosphate cladding of contrast experiment.
Fig. 8 is the structural representation of the aluminum phosphate clad anode active substance of prior art.
Main element symbol description
Anode composite material granule 10
Positive active material granule 12
Phosphoric acid aluminium lamination 14
Product 20
Little granule 22
Bulky grain 24
Detailed description of the invention
Below in conjunction with the accompanying drawings and the specific embodiments to the present invention provide cobalt acid lithium composite material granule and
Its preparation method, and lithium ion battery is described in further detail.
Referring to Fig. 1, the embodiment of the present invention provides a kind of anode composite material granule 10, and it includes positive pole
Active material particle 12 and be coated on the phosphoric acid aluminium lamination 14 of this positive active material particle surface.This phosphoric acid
The aluminium lamination 14 mass percent in this anode composite material granule 10 is 0.1% to 3%.This aluminum phosphate
The thickness of layer 14 is preferably 5 nanometers to 20 nanometers.This phosphoric acid aluminium lamination 14 is that in-situ preparation is at this positive pole
Active material particle 12 surface.This phosphoric acid aluminium lamination 14 be thickness uniformly and continuous print aluminum phosphate material layer.
Further, the interface between this phosphoric acid aluminium lamination 14 and this positive active material granule 12 is likely to be formed
Interface is spread, and makes cobalt atom diffuse in this phosphoric acid aluminium lamination 14.
The material of this positive active material granule 12 can be by chemical formula LixCo1-yMyO2,
LixMn1-yMyO2Or LixFe1-yMyPO4Represent, wherein 0.1≤x≤1.1,0≤y≤0.9, M selected from Mn,
At least one in Cr, Co, Ni, V, Ti, Al, Ga and Mg.Preferably, this positive electrode active material
The material of matter granule 12 is the cobalt acid lithium (Li of stratiformxCoO2), the LiMn2O4 (Li of stratiformxMnO2) or
Olivine-type LiFePO4 (LixFePO4)。
The embodiment of the present invention provides a kind of by aluminum phosphate coated lithium ion battery positive active material, forms institute
The method stating anode composite material granule 10, it comprises the following steps:
Step one, it is provided that aluminum nitrate solution；
Step 2, adds in this aluminum nitrate solution by positive active material granule to be covered, forms one and mixes
Compound；
Step 3, adds phosphate solution this mixture and reacts, makes this positive active material granule
Surface forms phosphoric acid aluminium lamination；And
Step 4, this surface of heat treatment has the positive active material granule of phosphoric acid aluminium lamination, obtains positive pole multiple
Condensation material granule.
This aluminum nitrate solution includes liquid phase solvent and is dissolved in the aluminum nitrate of this solvent.It is appreciated that this is molten
Agent is chosen as making aluminum nitrate dissociate and forms Al3+Solvent.Therefore this solvent is not limited to water, also may be used
Think volatile organic solvent, it is preferable that this solvent is in ethanol, acetone, dichloroethanes and chloroform
One or several mixing.Solvent is used water as relative to adopting, using organic solvent such as ethanol as solvent,
Positive active material granule and water can be avoided to react makes positive active material performance reduce.
In above-mentioned steps two, this positive active material granule does not dissolves in this aluminum nitrate solution, and both are solid
Liquid mixes, it is therefore an objective to uniformly adhere to one layer of Al on the surface of this positive active material granule3+.Due to Al3+
Exist in the form of an ion, positive active material particle surface can be attached to uniformly, to this positive-active
Material grains forms the cladding of atom level.Further, the addition of this positive active material can be controlled,
This positive active material granule is controllable to enable this aluminum nitrate solution to cover with the ratio of aluminum nitrate solution
Cover this positive active material particle surface can so as to get mixture be muddy.Formation muddy mixes
The purpose of compound is primarily to the addition controlling aluminum nitrate solution is just enough at positive active material
Grain surface forms one layer of aluminum phosphate clad.Specifically, the volume of this aluminum nitrate solution and this positive-active
The volume ratio of material grains is about 1: 10 to 1: 40.The particle diameter of this positive active material granule is the least
In 20 microns.The addition of this aluminum nitrate solution can account for positive pole by the aluminum phosphate clad that needs are formed
The mass percent of composite material granular is determined, it is preferable that this aluminum phosphate clad is multiple at this positive pole
Mass percent in condensation material granule is 0.1% to 3%.
In above-mentioned steps three, this phosphate solution includes that water, as solvent, and is dissolved in this solvent
Soluble phosphate, such as phosphoric acid ammonia salt.This phosphoric acid ammonia salt includes ammonium dihydrogen phosphate (NH4H2PO4), phosphoric acid
Hydrogen diammonium ((NH4)2HPO4) and triammonium phosphate ((NH4)3PO4The mixing of one or more in).This phosphoric acid
Containing phosphate anion in saline solution.This phosphate anion can be positive phosphorus acid ion (PO4 3-), phosphoric acid
Dihydro radical ion (H2PO4 -) and phosphoric acid one hydrogen radical ion (HPO4 2-The mixing of one or more in).This phosphorus
Acid salt solution add to described muddy mixture time, this phosphate anion be attached to positive active material
The Al of particle surface3+Reaction, thus it is formed in situ one layer of uniform phosphorus at positive active material particle surface
Acid aluminum precipitation.Preferably, this phosphate solution can be added dropwise over this muddy mixture, and is stirred
Mix, so that this phosphate anion and this Al3+Can be the most anti-at this positive active material particle surface
Should.With aluminum nitrate solution similarly, the aluminum phosphate that the addition of this phosphate solution can be formed by needs
Clad accounts for the mass percent of anode composite material granule and is determined.
In above-mentioned steps four, the purpose of this heat treatment is to make this aluminum phosphate and positive active material at interface
Place preferably combines, and forms composite, and removes the solvent of residual and react the ammonium nitrate generated.Logical
Cross this heat treatment, be likely to be formed interface diffusion in aluminum phosphate and positive active material interface, make cobalt atom
Diffuse in this phosphoric acid aluminium lamination.This heat treatment temperature can be 400 DEG C to 800 DEG C.This heat treatment time
Between be preferably 0.5 to 2 hour.
Owing to positive active material granule is first joined in aluminum nitrate solution by this method, then at this aluminum nitrate
Solution adds and can react the phosphate solution generating aluminum phosphate with aluminium ion, thus at positive electrode active material
One layer of continuous print phosphoric acid aluminium lamination of matter particle surface in-situ preparation.Aluminum nitrate solution and solid phase due to liquid phase
Positive active material granule mixes, and can first make aluminium ion be uniformly coated on this positive active material
Particle surface, therefore, the aluminum phosphate precipitation generated by aluminium ion after reaction in-situ also is able to evenly be coated with
On this positive active particles surface.With first synthesize aluminum phosphate granule, then make aluminum phosphate by adsorption
Grain is adsorbed onto the mode of positive active material particle surface and compares, and this method avoids owing to the most admittedly mixing
The absorption produced is uneven, causes the phenomenon that aluminum phosphate cladding is uneven, is suitable for heavy industrialization application.
It addition, this method can generate a layer thickness uniformly and continuous print aluminum phosphate at positive active material particle surface
Layer, rather than by aluminum phosphate particle packing at positive active material particle surface.This phosphoric acid aluminium lamination can every
Make ion pass through while electron transfer between electrolyte and active substance absolutely, thus complete lithium ion
Embedding and abjection while avoid electrolyte to decompose at higher voltages, therefore make this positive active material
Can have more preferable battery performance and capacity retention energy at higher voltages.
Embodiment
The present embodiment specifically uses said method to prepare institute by aluminum phosphate clad anode active material particle
State anode composite material granule, and this anode composite material granule is applied to Progressive symmetric erythrokeratodermia in lithium ion battery
Can test.This positive active material granule can be cobalt acid lithium or cation doping acid lithium granule, and the present embodiment is
Cobalt acid lithium granule.This aluminum phosphate-cobalt acid lithium composite material granule includes cobalt acid lithium granule and is coated on this cobalt
The phosphoric acid aluminium lamination of acid lithium particle surface.
In the preparation of this aluminum phosphate-cobalt acid lithium composite material granule, this aluminum nitrate solution is that aluminum nitrate exists
The solution formed in ethanol.The volume of this aluminum nitrate solution is 30 milliliters, molar concentration is 0.16 mole/
Rise.The addition of this cobalt acid lithium granule is 100g.This phosphate solution is (NH4)2HPO4Aqueous solution.
Being respectively 400 DEG C, 500 DEG C and 600 DEG C in heat treatment temperature, phosphoric acid aluminium lamination accounts for the percent mass of gross mass
Than being to prepare 3 kinds of aluminum phosphate-cobalt acid lithium composite material particulate samples under conditions of 1%.It addition,
Heat treatment temperature is 600 DEG C, and it is preparation under conditions of 1.5% that phosphoric acid aluminium lamination accounts for the mass percent of gross mass
Obtain a kind of aluminum phosphate-cobalt acid lithium composite material particulate samples.Refer to Fig. 2 and Fig. 3, the sample obtained
In, phosphoric acid aluminium lamination is uniformly coated on this cobalt acid lithium particle surface, by high magnification transmission electron microscope observing,
It can be clearly seen that this aluminum phosphate is to cover at this cobalt acid lithium with the form of material layer in uniform thickness
Grain surface.Respectively using these 4 kinds of samples as positive electrode active materials, with a certain proportion of conductive agent and
Binding agent mix homogeneously is coated on anode collection surface and makes positive pole, using metal lithium sheet as negative pole, and will
Positive pole and negative pole are spaced by barrier film and are assembled into lithium ion battery with electrolyte infiltration, carry out charge and discharge electrical
Can test.
Contrast experiment
Anode composite material granule for preparing with the embodiment of the present invention contrasts, with the side of prior art
Method prepares another comparative sample, concretely comprises the following steps:
By (NH4)2HPO4Aqueous solution mixes with aluminum nitrate aqueous solution, generates aluminum phosphate granule, shape in water
Become dispersion liquid；
Cobalt acid lithium granule is put in this dispersion liquid, makes aluminum phosphate granular absorption at cobalt by the effect of absorption
Acid lithium particle surface；And
At 600 DEG C, this surface adsorption of heat treatment has the cobalt acid lithium granule of aluminum phosphate granule, and it is described right to obtain
Compare sample.Refer to Fig. 4 and Fig. 5, by comparative sample prepared by art methods, aluminum phosphate
It is that the form of granule is gathered in this cobalt acid lithium particle surface, and aluminum phosphate agglomerate grain, makes cladding not
Uniformly.
Using this comparative sample as positive electrode active materials, under conditions of identical with the present embodiment, assemble electricity
Pond, carries out charge-discharge performance test.The most also using the cobalt acid lithium granule of uncoated any material as positive pole
Active material, is assembled into lithium ion battery under conditions of identical with the present embodiment, carries out charge-discharge performance
Test.Above-mentioned the present embodiment differs only in positive electrode active materials with contrast experiment's, other battery condition
And test condition is the most identical.
It is coated with the positive active material granule of aluminum phosphate, just improves owing to playing the aluminum phosphate of coating function
The surface texture of pole active material particle, provides de-deficient platform to lithium ion, simultaneously works as barrier layer
Effect, suppression tetravalence cobalt ion reacts with electrolyte effectively, stabilizes cobalt acid lithium structure, improves electricity
Chemical cycle performance.Refer to Fig. 6, above-mentioned 4 kinds of samples are carried out constant current charge-discharge under 0.5C electric current
Loop test, the blanking voltage of this charging is 4.5V, and the blanking voltage of electric discharge is 2.7V.Can from figure
To find, use sample prepared by the inventive method, owing to aluminum phosphate can be coated with cobalt acid aluminum uniformly
Grain, charging remains to have higher capacity and stable capability retention at higher voltages, 50 circulations
After capability retention all more than 90%, specific capacity is 160mAh/g to 175mAh/g.Further,
Along with the raising of heat treatment temperature, the capacity of battery increased.The change of this aluminum phosphate percentage composition is right
The impact of battery capacity is little.Refer to Fig. 7, this comparative sample and uncoated cobalt acid lithium particulate samples
Circulation volume the most drastically decline, the capability retention after 50 circulations is respectively less than 85%, and this is mainly
Owing to cobalt acid lithium particles coat is uneven or uncoated so that when being under high pressure charged, cobalt acid lithium with
Electrolyte reacts and makes the capacity of battery reduce.
It addition, those skilled in the art also can do other changes in spirit of the present invention, certainly, these depend on
The change done according to present invention spirit, within all should being included in scope of the present invention.
Claims (14)
1. a preparation method for cobalt acid lithium composite material granule, comprising:
Thering is provided aluminum nitrate solution, this aluminum nitrate solution includes volatile organic solvent and to be dissolved in this organic molten
The aluminum nitrate of agent；
Positive active material granule to be covered is added in this aluminum nitrate solution, the volume of this aluminum nitrate solution
Being 1:10 to 1:40 with the volume ratio of this positive active material granule, form muddy mixture, this is just
Pole active material particle is cobalt acid lithium or cation doping acid lithium granule；
Phosphate solution adds this mixture react, form phosphorus at this positive active material particle surface
Acid aluminium lamination；And
This surface of heat treatment has the positive active material granule of phosphoric acid aluminium lamination.
2. the preparation method of cobalt acid lithium composite material granule as claimed in claim 1, it is characterised in that this has
Machine solvent is ethanol.
3. the preparation method of cobalt acid lithium composite material granule as claimed in claim 1, it is characterised in that this phosphorus
Acid salt solution includes water and is dissolved in the phosphoric acid ammonia salt of water, and this phosphoric acid ammonia salt includes ammonium dihydrogen phosphate, phosphoric acid
The mixing of one or more in hydrogen diammonium and triammonium phosphate.
4. the preparation method of cobalt acid lithium composite material granule as claimed in claim 1, it is characterised in that this heat
Treatment temperature is 400 DEG C to 800 DEG C.
5. the preparation method of cobalt acid lithium composite material granule as claimed in claim 1, it is characterised in that this nitre
The volume of acid aluminum solutions is 30 milliliters, and the addition of this cobalt acid lithium granule is 100g.
6. a cobalt acid lithium composite material granule, by cobalt acid lithium composite material granule as claimed in claim 1
Preparation method prepare, this cobalt acid lithium composite material granule includes positive active material granule, this positive pole live
Property material grains is cobalt acid lithium or cation doping acid lithium granule, it is characterised in that farther include to be coated on this
The phosphoric acid aluminium lamination of positive active material particle surface, this aluminum phosphate layer thickness is uniform and continuous.
7. cobalt acid lithium composite material granule as claimed in claim 6, it is characterised in that this phosphoric acid aluminium lamination is at this
Mass percent in anode composite material granule is 0.1% to 3%.
8. cobalt acid lithium composite material granule as claimed in claim 6, it is characterised in that this phosphoric acid aluminium lamination is at this
Mass percent in anode composite material granule is 1% to 1.5%.
9. cobalt acid lithium composite material granule as claimed in claim 6, it is characterised in that the thickness of this phosphoric acid aluminium lamination
Degree is that 5 nanometers are to 20 nanometers.
10. cobalt acid lithium composite material granule as claimed in claim 6, it is characterised in that this phosphoric acid aluminium lamination is former
Position generates at this positive active material particle surface.
11. cobalt acid lithium composite material granules as claimed in claim 6, it is characterised in that this positive active material
The material of granule is by chemical formula LixCo1-yMyO2Represent, wherein 0.1≤x≤1.1,0≤y≤0.9, M be Mn,
At least one in Cr, V, Ti, Al, Ga and Mg.
12. 1 kinds of lithium ion batteries, it is characterised in that include positive pole, this positive pole includes as claimed in claim 7
Cobalt acid lithium composite material granule.
13. lithium ion batteries as claimed in claim 12, it is characterised in that be 4.5V at charge cutoff voltage,
Discharge cut-off voltage is the capacity that the scope of 2.7V carries out having more than 90% after constant current charge-discharge circulates 50 times
Conservation rate.
14. lithium ion batteries as claimed in claim 13, it is characterised in that be 4.5V at charge cutoff voltage,
Discharge cut-off voltage is that to carry out specific capacity after constant current charge-discharge circulates 50 times be 160mAh/g for the scope of 2.7V
To 175mAh/g.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010242531.3A CN102347470B (en) | 2010-08-02 | 2010-08-02 | Cobalt acid lithium composite material granule and preparation method thereof, and lithium ion battery |
| US13/092,135 US8568620B2 (en) | 2010-08-02 | 2011-04-21 | Electrode composite material, method for making the same, and lithium ion battery using the same |
| US13/106,996 US9054379B2 (en) | 2010-08-02 | 2011-05-13 | Electrode composite material, method for making the same, and lithium ion battery using the same |
| US13/106,994 US9219276B2 (en) | 2010-08-02 | 2011-05-13 | Electrode composite material, method for making the same, and lithium ion battery using the same |
| US13/107,006 US20120028120A1 (en) | 2010-08-02 | 2011-05-13 | Electrode composite material, method for making the same, and lithium ion battery using the same |
| US13/107,003 US9203087B2 (en) | 2010-08-02 | 2011-05-13 | Electrode composite material, method for making the same, and lithium ion battery using the same |
| US13/106,999 US8349494B2 (en) | 2010-08-02 | 2011-05-13 | Electrode composite material, method for making the same, and lithium ion battery using the same |
| US13/108,101 US8277979B2 (en) | 2010-08-02 | 2011-05-16 | Electrode composite material, method for making the same, and lithium ion battery using the same |
| JP2011146855A JP5449265B2 (en) | 2010-08-02 | 2011-06-30 | ELECTRODE COMPOSITE MATERIAL, ITS MANUFACTURING METHOD, AND LITHIUM ION BATTERY USING THE SAME |
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| CN102456868B (en) * | 2010-11-03 | 2014-03-26 | 清华大学 | Lithium titanate composite material and preparation method thereof and lithium ion battery |
| CN105144438B (en) * | 2013-05-07 | 2018-05-15 | 同和控股（集团）有限公司 | Positive electrode active material powder and its manufacture method |
| JP5807730B1 (en) * | 2015-03-04 | 2015-11-10 | 宇部興産株式会社 | Lithium titanate powder and active material for electrode of power storage device, and electrode sheet and power storage device using the same |
| CN109980189A (en) * | 2017-12-27 | 2019-07-05 | 荆门市格林美新材料有限公司 | A kind of nickel cobalt lithium aluminate cathode material and preparation method thereof coating aluminum phosphate |
| CN112510184B (en) * | 2021-02-04 | 2021-06-25 | 浙江大学 | Lithium ion battery anode material and preparation method thereof |
| WO2023175731A1 (en) * | 2022-03-15 | 2023-09-21 | 株式会社 東芝 | Electrode, battery, and battery pack |
| CN115504445A (en) * | 2022-11-08 | 2022-12-23 | 南木纳米科技(北京)有限公司 | Aluminum phosphate material and preparation method thereof |
| CN117254020B (en) * | 2023-11-13 | 2024-03-08 | 江门市科恒实业股份有限公司 | Aluminum phosphate coated calcium-doped sodium ion battery positive electrode material and preparation method thereof |
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| Joon-Gon Lee et.al.Effect of AlPO4-nanoparticle coating concentration on high-cutoff-voltage electrochemical performances in LiCoO2.《Journal of the electrochemical society》.2004,第151卷(第6期),A801-A805. * |
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| JP5449265B2 (en) | 2014-03-19 |
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