CN110098384A - A kind of modified cobalt acid lithium and its preparation and application - Google Patents
A kind of modified cobalt acid lithium and its preparation and application Download PDFInfo
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- CN110098384A CN110098384A CN201810085555.9A CN201810085555A CN110098384A CN 110098384 A CN110098384 A CN 110098384A CN 201810085555 A CN201810085555 A CN 201810085555A CN 110098384 A CN110098384 A CN 110098384A
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention relates to a kind of modified cobalt acid lithium and its preparations and application, obtain the modification cobalt acid lithium of electrochemical performance and coating cobalt acid lithium with a certain amount of nanoscale LiMn2O4；Cobalt acid lithium method of modifying simple process provided by the invention is suitble to large-scale industrial production；Modified cobalt acid lithium provided by the invention is used for the positive electrode of lithium ion battery, and makes cycle performance of lithium ion battery excellent.
Description
Technical field
The present invention relates to a kind of positive electrodes of lithium ion battery, and in particular to a kind of modification of cobalt acid lithium and modified cobalt acid
The application of lithium.
Background technique
Cobalt acid lithium has good chemical property and mature production technology, is the maximum lithium ion cell positive of usage amount
One of material.The theoretical specific capacity of cobalt acid lithium is 274mAh/g, but due to the structural instability of stratiform cobalt acid lithium, in over-discharge
When, layer structure can collapse, and form Spinel, the insertion of lithium ion when hindering to charge, so that its actual specific capacity
Only 120-140mAh/g.The actual specific capacity for improving cobalt acid lithium, can be improved charge cutoff voltage, but this can accelerate cobalt acid lithium
Structure destroys that cycle life is greatly reduced.In order to improve the energy density of cobalt acid lithium, while in order to solve to fill in high voltage
The volume change, the problem that oxidation is precipitated and the dissolution of cobalt causes its capacity attenuation fast of phase change generation, need in discharge process
Cobalt acid lithium is more studied.
Therefore, it needs a kind of modified cobalt acid lithium and preparation method thereof and makes that the energy density of cobalt acid lithium is high, structure is more steady
Calmly, preparation method is simple, while improving the cycle performance of material.
Summary of the invention
In order to overcome the above problem, the present inventor has done sharp study, designs a kind of modified cobalt acid lithium, by with certain
The nanoscale LiMn2O4 of amount coats cobalt acid lithium and obtains the modification cobalt acid lithium of electrochemical performance；Cobalt acid lithium provided by the invention
Method of modifying simple process is suitble to large-scale industrial production, so as to complete the present invention.
In particular it is object of the present invention to provide following aspect:
In a first aspect, providing a kind of modified cobalt acid lithium, the modification is formed by lithium salts cladding cobalt acid lithium, the lithium salts
Including LiFePO4, LiMn2O4, lithium nickelate, phosphoric acid vanadium lithium, preferably LiMn2O4.
Second aspect provides a kind of preparation method of modified cobalt acid lithium, comprising the following steps:
1) it feeds；
2) it is mixed under setting condition；
3) it is sintered under setting condition, obtains final product.
The third aspect provides a kind of purposes of modified cobalt acid lithium, it is preferable that its positive material for being applied to lithium ion battery
Material is used as the lithium ion battery of positive electrode preparation within the scope of 3.0V-4.5V, and after circulation 50 times, capacity retention ratio still may be used
Up to 94%, cyclical stability is more preferable.
Beneficial effect possessed by the present invention includes:
(1) the modification cobalt acid lithium provided according to the present invention is embedding by coating one layer of lithium manganate having spinel structure on cobalt acid lithium surface
The cobalt acid lithium entered can prevent active material and electrolyte from directly contacting, to reduce crystal structure caused by the dissolution of internal cobalt
Destruction；
(2) the modification cobalt acid lithium provided according to the present invention is embedded in by the lithium manganate having spinel structure formed on cobalt acid lithium surface
Cobalt acid lithium can reduce the strain differential of ectonexine in charge and discharge process, reduce structure and destroy；
(3) the modification cobalt acid lithium provided according to the present invention is within the scope of 3.0V-4.5V, after circulation 50 times, capacity retention ratio
Still up to 94%, modified material has good electrochemical cycle stability under high voltages；
(4) the preparation method technical process of the modification cobalt acid lithium provided according to the present invention is simple, and is evenly coated, and is suitble to
Produce in enormous quantities.
Detailed description of the invention
Fig. 1 shows the SEM figure of pure phase cobalt acid lithium；
Fig. 2 shows the SEM of the resulting modified cobalt acid lithium of embodiment 1 figures；
Fig. 3 shows the cycle performance curve graph of pure phase cobalt acid lithium and the resulting modified cobalt acid lithium of Examples 1 to 5.
Specific embodiment
Below by drawings and examples, the present invention is described in more detail.Illustrated by these, the features of the present invention
It will be become more apparent from advantage clear.
Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.Here as " exemplary "
Illustrated any embodiment should not necessarily be construed as preferred or advantageous over other embodiments.Although each of embodiment is shown in the attached drawings
In terms of kind, but unless otherwise indicated, it is not necessary to attached drawing drawn to scale.
A kind of modified cobalt acid lithium provided according to the present invention, the modified cobalt acid lithium are to coat cobalt acid lithium matrix shape by lithium salts
At；
The lithium salts includes LiFePO4, LiMn2O4, lithium nickelate, phosphoric acid vanadium lithium；
The lithium salts is LiMn2O4, and the LiMn2O4 is the LiMn2O4 of Spinel, the LiMn2O4 of high-voltage spinel phase
One of with layered lithium manganate, it is preferable that the lithium salts is nanoscale；
Since nineteen ninety SONY is used and can be done positive electrode with the cobalt acid lithium of embedding lithium, lithium cobaltate cathode material relies on it
The advantages that voltage is high, electric discharge is steady, simple production process in occupation of market main status and currently the only be largely used to give birth to
Produce the positive electrode of lithium ion battery.
But cobalt acid lithium, there are still many disadvantages, security performance is slightly worse, and cycle performance is undesirable, and discharge capacity is remote
Not up to theoretical value, theoretical gram volume is 274mAh/g, and the gram volume of existing cobalt acid lithium in the market only has 145mAh/g or so.Together
When, since cobalt resource lacks, expensive, lithium ion cell anode material lithium cobaltate is because of the factors such as at high cost, constrain cobalt acid
Lithium is applied and is developed in the market.
Cobalt acid lithium (LiCoO2) there are three types of object phases, the i.e. HT-LiCoO of layer structure for tool2, the LT-LiCoO of spinel structure2
With rock salt phase LiCoO2.Applying in lithium ion battery at present at most is stratiform cobalt acid lithium, and structure is more stable.
The actual specific capacity of cobalt acid lithium is low, and during repeated charge, and active material configuration is shunk and swollen multiple
It changes after swollen, causes cobalt acid lithium to occur to loosen and fall off, internal resistance is caused to increase, capacity reduces.Its basic reason is cobalt
Sour lithium is the intercalation compounds of lithium ion, if lithium ion (more than half) excessive when charging is deviate from from cobalt acid lithium, cobalt
Sour lithium can occur crystal form and change and no longer have the function of being embedded in and deviating from lithium ion.
In order to further improve the performance of cobalt acid lithium material, coating modification research is carried out to cobalt acid lithium, keeps its charge and discharge electrical
Energy, cycle performance are improved.
And LiMn2O4 is one of more promising lithium ion anode material, compared to traditional positive electrode such as cobalt acid lithium, mangaic acid
Lithium has many advantages, such as that resourceful, at low cost, pollution-free, safety is good, good rate capability, is ideal power battery anode material
Material, but its poor cycle performance and electrochemical stability greatly limit its industrialization.LiMn2O4 mainly includes spinelle
Type (phase) LiMn2O4 and layer structure LiMn2O4, wherein lithium manganate having spinel structure stable structure, it is easy to accomplish industrialized production, such as
Modern market product is such structure.Lithium manganate having spinel structure belongs to cubic system, Fd3m space group, and theoretical specific capacity is
148mAh/g, due to three-dimensional tunnel structure, lithium ion can the reversibly deintercalation from spinel crystal lattice, structure will not be caused
Collapse, thus have excellent high rate performance and stability.
Inventors believe that LiMn2O4 is since with three-dimensional tunnel structure, lithium ion can be reversibly from spinel crystal lattice
Middle deintercalation will not cause collapsing for structure, and when LiMn2O4 is coated on cobalt acid lithium surface, this design feature of LiMn2O4 can be with
The strain differential of ectonexine in cobalt acid lithium charge and discharge process is reduced, cobalt acid lithium structure is reduced and destroys, to improve modified cobalt acid lithium
Electrochemistry cycle performance.
The present inventor is also believed that the cobalt acid lithium for coating the insertion of one layer of spinel-type (phase) LiMn2O4 on cobalt acid lithium surface can be with
Prevent active material cobalt acid lithium and electrolyte from directly contacting, so that the destruction of crystal structure caused by the dissolution of internal cobalt is reduced,
So as to improve the electrochemistry cycle performance of modified cobalt acid lithium.
The present invention also provides a kind of preparation methods of modified cobalt acid lithium, comprising the following steps:
Step 1: charging；
Step 2: being mixed under setting condition；
Step 3: being sintered under setting condition, post-process, obtain final product.
Step 1, it feeds；
The charging includes that cobalt acid lithium and lithium salts is added, and the lithium salts is LiFePO4, LiMn2O4, lithium nickelate, vanadium phosphate
Lithium, preferably LiMn2O4, it is highly preferred that the LiMn2O4 is the LiMn2O4 of Spinel, the LiMn2O4 of high-voltage spinel phase
One of with layered lithium manganate,
Preferably, the lithium salts is nanoscale；
It is highly preferred that the lithium salts average grain diameter is 50nm~1500nm；
The lithium salts and the mass ratio of cobalt acid lithium are 1:(20~1000)；
It is further preferred that
The lithium salts average grain diameter is 10nm~1000nm；
The lithium salts and the mass ratio of cobalt acid lithium are 1:(30~900).
In the present invention, the median particle diameter (d50) of the cobalt acid lithium matrix is 8-12 μm, and modified cobalt acid lithium, which coats, uses lithium salts
Average grain diameter be 50nm~1500nm, preferably 100nm~1000nm；
In one preferred embodiment, nanoscale LiMn2O4 be added coats cobalt acid lithium matrix, the nanoscale manganese
Sour lithium average grain diameter is 100nm~1000nm.
The inventors discovered that be easy to causeing reunion existing when the nanoscale LiMn2O4 average grain diameter being added is less than 100nm
As so that cladding is uneven, obtained cladding product electrical property is poor；When the nanoscale LiMn2O4 partial size being added is greater than
When 1000nm, LiMn2O4 cladding cobalt acid lithium product cannot be obtained, the modification cobalt acid lithium of preferable electrical property cannot be obtained.
In one preferred embodiment, institute's cladding with the mass ratio of nanoscale LiMn2O4 and cobalt acid lithium be 1:(30~
900), when LiMn2O4 used is too high or too low, then the cycle performance of the modification cobalt acid lithium obtained can all reduce.
In further preferred embodiment, institute's cladding is 1:(50 with the mass ratio of nanoscale LiMn2O4 and cobalt acid lithium
~850).
The inventors discovered that the present invention preferably does additive cladding cobalt acid lithium, obtained modified cobalt acid lithium with LiMn2O4
It has excellent performance.Although LiFePO4, lithium nickelate, phosphoric acid vanadium lithium are also relatively common lithium salts, but, for coating cobalt acid lithium institute
Obtained modification cobalt acid lithium effect is all not so good as the modification cobalt acid lithium that LiMn2O4 coats.For example, with LiFePO4 cladding cobalt acid
Lithium, first process needs carry out in stringent reduction inert atmosphere, operate relatively difficult；If furthermore being exactly Fe with three
The form of valence iron exists, then surface resultant may have adverse effect on lithium cobaltate cathode material；In addition, LiFePO4 is viscous
Spend it is larger, disperse it is very bad, agglomeration is serious；Finally, LiFePO4 viscosity is larger, wall built-up is serious, causes quantitative cladding tired
It is difficult.Therefore, the inventors discovered that, the obtained modified cobalt acid lithium electricity of cobalt acid lithium is coated with the nanoscale LiMn2O4 of additive amount
Chemical cycle performance is best.
Step 2, it is mixed under setting condition；
Described be mixed into mixes in a high speed mixer；
The mixed speed is 100~1200rpm, preferably 300~1000rpm；
The mixed time is 5~30min, preferably 8~20min；
The mixed temperature is room temperature.
Step 3, it is sintered under setting condition, post-processes, obtain final product.
The sintering temperature is 500~1000 DEG C, preferably 600~900 DEG C；
The sintering time is 3~12h, preferably 4~10h；
The post-processing includes Temperature fall.
In one preferred embodiment, sintering temperature is 600~900 DEG C, and sintering time is 4~10h.
The inventors discovered that the cobalt acid lithium particle after cladding, needs to be sintered at a suitable temperature, cladding is produced
Object can just show the normal and excellent performance of comparison；If sintering temperature is too low, cladding product modification cobalt acid lithium is unable to shape
At good lattice, product property is poor；If sintering temperature is too high, the lithia Li on modified cobalt acid lithium surface2O can be generated and be waved
Hair destroys cobalt acid lithium plane of crystal, and lattice forms defect, causes modified cobalt acid lithium reduced performance.The selection of sintering time length
It is also same reason.
The third aspect, the present invention also provides the purposes of the modification cobalt acid lithium, which is characterized in that the modified cobalt acid lithium
Positive electrode applied to lithium ion battery；The modified cobalt acid lithium is used as the lithium ion battery of positive electrode preparation in 3.0V-
In 4.5V, after circulation 50 times, capacity retention ratio is still up to 94%.
Present invention has an advantage that (1) can in the cobalt acid lithium that cobalt acid lithium surface coats the insertion of one layer of lithium manganate having spinel structure
To prevent active material and electrolyte from directly contacting, to reduce the destruction of crystal structure caused by the dissolution of internal cobalt.(2) exist
The cobalt acid lithium for the lithium manganate having spinel structure insertion that cobalt acid lithium surface is formed can reduce the strain differential of ectonexine in charge and discharge process,
Structure is reduced to destroy.(3) technical process is simple, is suitble to produce in enormous quantities, and be evenly coated, modified material is under high voltages
With good electrochemical cycle stability.
Embodiment
The present invention is further described below by way of specific example.But these examples are only exemplary, not to this
The protection scope of invention constitutes any restrictions.
Embodiment 1
100g cobalt acid lithium and 0.25g lithium manganate having spinel structure are put into high-speed mixer with 500rpm mixing 15min, it is complete
It at rear taking-up, is placed in mullite crucible, is sintered 5 hours for 800 DEG C in ceramic fibre Muffle furnace, is modified after Temperature fall
Cobalt acid lithium.
Embodiment 2
100g cobalt acid lithium and 0.5g high-voltage spinel type LiMn2O4 are put into high-speed mixer and are mixed with 500rpm
15min takes out after the completion, is placed in mullite crucible, is sintered 5 hours for 800 DEG C in ceramic fibre Muffle furnace, after Temperature fall
Obtain modified cobalt acid lithium.
Embodiment 3
100g cobalt acid lithium and 0.25g high-voltage spinel type LiMn2O4 are put into high-speed mixer and are mixed with 500rpm
15min takes out after the completion, is placed in mullite crucible, is sintered 7 hours for 800 DEG C in ceramic fibre Muffle furnace, after Temperature fall
Obtain modified cobalt acid lithium.
Embodiment 4
100g cobalt acid lithium and 0.125g high-voltage spinel type LiMn2O4 are put into high-speed mixer and are mixed with 500rpm
15min takes out after the completion, is placed in mullite crucible, is sintered 7 hours for 800 DEG C in ceramic fibre Muffle furnace, after Temperature fall
Obtain modified cobalt acid lithium.
Embodiment 5
100g cobalt acid lithium and 0.125g high-voltage spinel type LiMn2O4 are put into high-speed mixer and are mixed with 800rpm
15min takes out after the completion, is placed in mullite crucible, is sintered 7 hours for 800 DEG C in ceramic fibre Muffle furnace, after Temperature fall
Obtain modified cobalt acid lithium.
Experimental example
The SEM figure of 1 pure phase cobalt acid lithium of experimental example and modified cobalt acid lithium
The SEM of pure phase cobalt acid lithium shown in Fig. 1 (i.e. cobalt acid lithium matrix) schemes；
Fig. 2 shows the SEM figures of modified cobalt acid lithium obtained by embodiment 1；
Electronic Speculum test is scanned to the modification cobalt acid lithium that pure phase cobalt acid lithium and embodiment 1 obtain, as a result such as Fig. 1 and Fig. 2
Shown, can be learnt by above-mentioned test result: the partial size for the coating modification cobalt acid lithium that the present invention is prepared is smaller and uniform.
The performance test of 2 pure phase cobalt acid lithium of experimental example and modified cobalt acid lithium
2.1 prepare lithium ion battery
By pure phase cobalt acid lithium and the LiMn2O4 synthesized using method of the invention cladding lithium cobaltate cathode material respectively with lead
Electrical carbon is black and binder polyvinylidene fluoride (PVDF) 90:5:5 in mass ratio is uniformly mixed, and is coated on aluminium foil, is cut into after dry
Anode pole piece is dried in vacuo 10 hours in 100 DEG C.It is to electrode, high-voltage electrolyte is commercialized as electrolysis with lithium metal
Liquid, on argon gas gloves in be assembled into button cell.
2.2 electrochemical property test
Electrochemical property test, charge voltage range 3.0V- are carried out using the blue electricity CT2001A type cell tester in Wuhan
4.5V(vc.Li+/ Li), test result is shown in Table shown in 1 and Fig. 3.Wherein, in Fig. 3,
0# shows the cycle performance curve of pure phase cobalt acid lithium；
1# shows the cycle performance curve of the product of embodiment 1；
2# shows the cycle performance curve of the product of embodiment 2；
3# shows the cycle performance curve of the product of embodiment 3；
4# shows the cycle performance curve of the product of embodiment 4；
5# shows the cycle performance curve of the product of embodiment 5.
The cycle performance data of table 1 embodiment product and pure phase cobalt acid lithium
As table 1 and Fig. 3 result it is found that 50 circulation volume conservation rates of modification cobalt acid lithium obtained by Examples 1 to 5 are remote
Much higher than the capacity retention ratio of pure phase cobalt acid lithium, the modification cobalt acid lithium that the present invention is prepared as a result, has excellent electrochemistry
Cycle performance.
Modified cobalt acid lithium provided by the invention coats the lithium manganate having spinel structure of one layer of additive capacity, manganese on cobalt acid lithium surface
The cobalt acid lithium of sour lithium insertion can prevent active material cobalt acid lithium and electrolyte from directly contacting, so that the dissolution for reducing internal cobalt is led
The destruction of the crystal structure of cause；And it can reduce and fill in the cobalt acid lithium for the lithium manganate having spinel structure insertion that cobalt acid lithium surface is formed
The strain differential of ectonexine in discharge process reduces structure and destroys；And present invention process process is simple, is suitble to produce in enormous quantities,
And be evenly coated, modified material has good electrochemical cycle stability under high voltages.
Combining preferred embodiment above, the present invention is described, but these embodiments are only exemplary
, only play the role of illustrative.On this basis, a variety of replacements and improvement can be carried out to the present invention, these each fall within this
In the protection scope of invention.
Claims (10)
1. a kind of modified cobalt acid lithium, which is characterized in that the modified cobalt acid lithium is formed by lithium salts cladding cobalt acid lithium matrix.
2. modified cobalt acid lithium according to claim 1, which is characterized in that the lithium salts includes LiFePO4, LiMn2O4, nickel
Sour lithium, phosphoric acid vanadium lithium.
3. modified cobalt acid lithium according to claim 2, which is characterized in that the lithium salts is LiMn2O4, and the LiMn2O4 is
The LiMn2O4 of Spinel, one of LiMn2O4 and layered lithium manganate of high-voltage spinel phase,
Preferably, the lithium salts is nanoscale lithium salts.
4. a kind of preparation method of modified cobalt acid lithium, which comprises the following steps:
Step 1: charging；
Step 2: being mixed under setting condition；
Step 3: being sintered under setting condition, post-process, obtain final product.
5. the preparation method according to claim 4, which is characterized in that in step 1,
The charging includes that cobalt acid lithium and lithium salts is added, and the lithium salts is selected from LiFePO4, LiMn2O4, lithium nickelate and phosphoric acid
One of vanadium lithium is a variety of, preferably LiMn2O4, it is highly preferred that the LiMn2O4 is LiMn2O4, the high voltage of Spinel
One of LiMn2O4 and layered lithium manganate of Spinel,
Preferably, the lithium salts is nanoscale lithium salts.
6. preparation method according to claim 5, which is characterized in that in step 1,
The lithium salts average grain diameter is 50nm~1500nm；
The lithium salts and the mass ratio of cobalt acid lithium are 1:(20~1000)；
Preferably,
The lithium salts average grain diameter is 100nm~1000nm；
The lithium salts and the mass ratio of cobalt acid lithium are 1:(30~900).
7. the preparation method according to claim 4, which is characterized in that in step 2,
Described be mixed into mixes in a high speed mixer；
The mixed speed is 100~1200rpm, preferably 300~1000rpm；
The mixed time is 5~30min, preferably 8~20min.
8. the preparation method according to claim 4, which is characterized in that in step 3,
The sintering temperature is 500~1000 DEG C, preferably 600~900 DEG C；
The sintering time is 3~12h, preferably 4~10h；
The post-processing is Temperature fall.
9. the purposes of modified cobalt acid lithium according to any one of claims 1 to 3, which is characterized in that the modified cobalt acid lithium is answered
Positive electrode for lithium ion battery.
10. the purposes of modified cobalt acid lithium according to claim 8, which is characterized in that
The modified cobalt acid lithium is used as the lithium ion battery of positive electrode preparation in 3.0V-4.5V, and after circulation 50 times, capacity is protected
Holdup is still up to 94%.
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| CN112151779A (en) * | 2020-09-18 | 2020-12-29 | 深圳市贝特瑞纳米科技有限公司 | Binary anode composite material and preparation method and application thereof |
| CN112750998A (en) * | 2020-12-23 | 2021-05-04 | 无锡晶石新型能源股份有限公司 | Process method for coating spinel lithium manganate with spherical lithium manganate |
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| CN112151779A (en) * | 2020-09-18 | 2020-12-29 | 深圳市贝特瑞纳米科技有限公司 | Binary anode composite material and preparation method and application thereof |
| CN112750998A (en) * | 2020-12-23 | 2021-05-04 | 无锡晶石新型能源股份有限公司 | Process method for coating spinel lithium manganate with spherical lithium manganate |
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