CN107394166A - Nickel-cobalt lithium manganate cathode material of high security double-coating and preparation method thereof - Google Patents
Nickel-cobalt lithium manganate cathode material of high security double-coating and preparation method thereof Download PDFInfo
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- CN107394166A CN107394166A CN201710616454.5A CN201710616454A CN107394166A CN 107394166 A CN107394166 A CN 107394166A CN 201710616454 A CN201710616454 A CN 201710616454A CN 107394166 A CN107394166 A CN 107394166A
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Abstract
The present invention discloses a kind of nickel-cobalt lithium manganate cathode material of high security double-coating and preparation method thereof, and the positive electrode, kernel is nickle cobalt lithium manganate, in addition to：Internal layer covering material V2O5, external sheath material is conductive polymer polymer.The present invention can form the uniform clad of two layers of thickness, internal layer V on positive electrode active materials material grainses surface2O5, outer layer is conducting high polymers thing.Relative to other inorganic matters, V2O5With higher ionic conductivity, while LiOH, Li in preparation process with NCM material surfaces2CO3Reaction forms LiVO3, avoid the HF in positive electrode and electrolyte from reacting.On the one hand electronics that the conducting high polymers thing of outer layer can improve material passes to characteristic, on the other hand can avoid loss of the V element in the long-term cyclic process of battery again, improve stability test.
Description
Technical field
The invention belongs to technical field of lithium batteries, more particularly to a kind of nickle cobalt lithium manganate positive pole of high security double-coating
Material and preparation method thereof.
Background technology
Lithium ion battery due to the clear superiority with high-energy-density and high-specific-power, and be considered as it is most potential not
Carry out electrokinetic cell system, but it is on fire to be especially related to lithium ion battery explosion there is also certain safety issue often for it
Report, largely govern its use on vehicle electric system.
Improved constantly with the energy density of batteries of electric automobile, ternary nickel cobalt manganese material is widely applied, and is
Raising energy density, the increase of nickel content, makes the heat endurance of material reduce, the security performance of battery is deteriorated in material.Heat
Out of control is ternary lithium battery most one of urgent problem.By positive electrode, caused thermal runaway behavior will aggravate to be electrolysed in itself
The decomposition of liquid and the oxidation of barrier film, so as to cause potential potential safety hazard.
In order to solve the problems, such as above-mentioned thermal runaway, it is usually taken in one layer of inorganic matter thing of tertiary cathode material Surface coating such as
Al2O3、SiO2、 ZrO2、TiO2、AlPO4、Li2ZrO3Or AlF3To improve the heat endurance of tertiary cathode material.Inorganic matter coats
The stability of tertiary cathode material can be improved, but because inorganic matter reduces lithium ion conductivity, adds interface resistance, so as to
Reduce battery performance.
Therefore, there is problem, it is necessary to further improve in prior art.
The content of the invention
The problem of existing for prior art inorganic matter cladding, the present invention provides a kind of nickel cobalt of high security double-coating
LiMn2O4（NCM）Positive electrode and preparation method thereof.
First, the present invention provides a kind of nickel-cobalt lithium manganate cathode material of high security double-coating, concrete technical scheme
It is as follows：A kind of nickel-cobalt lithium manganate cathode material of high security double-coating, kernel is nickle cobalt lithium manganate, in addition to：Internal layer bag
Cover material V2O5, external sheath material is conductive polymer polymer.
Preferably, the conductive polymer polymer be selected from polypyrrole, poly- 3,4-rthylene dioxythiophene, poly- butyl thiophene,
Any one in poly- 3- hexyl thiophenes.
Preferably, internal layer cladding thickness is 0.01-30nm, and external sheath thickness is 5-300nm.
Secondly, the present invention also provides the preparation method of above-mentioned positive electrode, comprises the steps of：
（a）The preparation of kernel nickle cobalt lithium manganate particle
Nickel sulfate, cobaltous sulfate and manganese sulfate are made into mixed solution according to Ni:Co:Mn mol ratios are 0.5:0.2:0.3 mixing is equal
Even, the total mole number of tri- kinds of transition metal ions of Ni, Co, Mn is 2mol/L, then by 4mol/L NaOH solution and
Transition metal ion solution and 4mol/L ammoniacal liquor are added in reaction vessel simultaneously, and the pH values for controlling reaction system are
11.5, reaction temperature is 60 DEG C, and the control reaction time causes the Ni of generation0.5Co0.2Mn0.3(OH)2Particle diameter D50 be 3.5 μ
M, particle diameter distribution meet normal distribution；Then by after the filtering of obtained precipitation, washing, dried 12 hours at 120 DEG C；
By lithium carbonate and Ni0.5Co0.2Mn0.3(OH)2According to Li/X=1.05 (X=Ni0.5Co0.2Mn0.3(OH)2 ) ratio enter
Row mixing, be well mixed after, in Muffle furnace 800 DEG C calcining 12h, atmosphere be 3L/min oxygen, material furnace cooling,
300 mesh sieves are crossed after crushing；
（b）Internal layer coats V2O5
Configure 1mg/ml NH4VO3The aqueous solution, by step（a）NCM and NH4VO3Solution mixes, and is constantly stirred under the conditions of 80 DEG C
Mix evaporative removal and obtain NH4VO3 cladding NCM, alum acid ammonium content is 0.01-5%, and NH4VO3 is coated into NCM in Muffle furnace afterwards
600 DEG C of roasting 3h obtain V2O5Coat NCM；
（c）External sheath conductive polymer polymer
V2O5Cladding NCM, conducting polymer monomer and paratoluenesulfonic acid sodium salt are uniformly mixed in absolute ethyl alcohol, FeCl3As
Oxidant is constantly instilled in mixture, and mixture is stirred continuously 24h under the conditions of ice-water bath and carries out polymerisation；React afterwards
Product filtering, washing are simultaneously dried in vacuo 12h at 80 DEG C, obtain conducting polymer-VO-NCM.
The present invention can form the uniform clad of two layers of thickness on positive electrode active materials material grainses surface, and internal layer is
V2O5, outer layer are conducting high polymers thing.Relative to other inorganic matters, V2O5With higher ionic conductivity, while
In preparation process and NCM material surfaces LiOH, Li2CO3Reaction forms LiVO3, avoid the HF in positive electrode and electrolyte from sending out
Raw reaction.On the one hand electronics that the conducting high polymers thing of outer layer can improve material passes to characteristic, on the other hand can keep away again
Exempt from loss of the V element in the long-term cyclic process of battery, improve stability test.
Brief description of the drawings
Fig. 1 is V in NCM, comparative example 2 in comparative example 12O5Coat P3BT and V in NCM, embodiment 12O5Double-coating NCM
XRD spectrum；
Fig. 2 is V in NCM (a), comparative example 2 in comparative example 12O5P3BT cladding NCM (b) in NCM (c), comparative example 3 are coated to implement
P3BT and V in example 12O5Double-coating NCM (d)；
Fig. 3 is V in NCM, comparative example 2 in embodiment 12O5Coat P3BT in NCM, comparative example 3 and coat P3BT in NCM embodiments 1
And V2O5The high rate performance of double-coating NCM half-cells compares；
Fig. 4 is V in NCM, comparative example 2 in comparative example 12O5Coat P3BT in NCM, comparative example 3 and coat P3BT in NCM embodiments 1
And V2O5Cycle performance of the double-coating NCM material half-cell under the conditions of 0.5C；
Fig. 5 is V in NCM, comparative example 2 in comparative example 12O5Coat P3BT in NCM, comparative example 3 and coat P3BT in NCM embodiments 1
And V2O5Double-coating NCM half-cells 100 are charged to the differential thermometric analysis figure of de- lithium NCM materials after 4.3V after circulating.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further described.
Embodiment 1
V2O5Coat NCM, butyl thiophene（3BT）It is uniformly mixed with paratoluenesulfonic acid sodium salt in absolute ethyl alcohol, FeCl3As
Oxidant is constantly instilled in mixture, and mixture is stirred continuously 24h under the conditions of ice-water bath and carries out polymerisation.React afterwards
Product filtering, washing are simultaneously dried in vacuo 12h at 80 DEG C, obtain P3BT-VO-NCM.
P3BT-VO-NCM, acetylene black, KS-6, PVDF are mixed according to the ratio that mass ratio is the ︰ 0.3 of 9.2 ︰, 0.3 ︰ 0.2
Uniformly, appropriate NMP is added, uniform slurry is made in stirring；Slurry is uniformly applied on aluminium foil, is put into air dry oven
After drying, 120 DEG C of vacuum drying 12h of vacuum drying chamber are placed into；After natural cooling a diameter of 16mm is gone out with sheet-punching machine
Disk, disk is placed on tablet press machine with obtaining positive plate after 10MPa pressure compaction.Using homemade positive plate as just
Pole, lithium piece are negative pole, and Celgard2400 microporous polypropylene membranes are barrier film, 1mol/L LiPF6/EC+DMC (v:V=1:
1) it is electrolyte, CR2016 is assembled into the gloves phase full of argon gas of water content and oxygen content all in below 0.1ppm
Type experimental cell.
Carry out constant current charge-discharge test at room temperature, the test voltage scope of high rate performance is 2.6V~4.3V, charge and discharge
Electric multiplying power is 0.1C, 0.2C, 0.5C, 1.0C, 2.0C, 5.0C each 5 times, is finally circulated 5 times under 0.1C.Cycle performance
The voltage range of test is also 2.6V~4.3V, is circulated 100 times under 0.5C.
Embodiment 2
Material and battery preparation technique are similar to Example 1, and conducting polymer monomer is pyrroles.
Carry out constant current charge-discharge test at room temperature, the test voltage scope of high rate performance is 2.6V~4.3V, charge and discharge
Electric multiplying power is 0.1C, 0.2C, 0.5C, 1.0C, 2.0C, 5.0C each 5 times, is finally circulated 5 times under 0.1C.Cycle performance
The voltage range of test is also 2.6V~4.3V, is circulated 100 times under 0.5C.Electro-chemical test 0.5C discharge capacities first
For 170.2mAh/g.
Embodiment 3
Material and battery preparation technique are similar to Example 1, and conducting polymer monomer is 3- hexyl thiophenes.
Carry out constant current charge-discharge test at room temperature, the test voltage scope of high rate performance is 2.6V~4.3V, charge and discharge
Electric multiplying power is 0.1C, 0.2C, 0.5C, 1.0C, 2.0C, 5.0C each 5 times, is finally circulated 5 times under 0.1C.Cycle performance
The voltage range of test is also 2.6V~4.3V, is circulated 100 times under 0.5C.Electro-chemical test 0.5C discharge capacities first
For 170.1 mAh/g.
Embodiment 4
Material and battery preparation technique are similar to Example 1, and conducting polymer monomer is 3,4-rthylene dioxythiophene.
Carry out constant current charge-discharge test at room temperature, the test voltage scope of high rate performance is 2.6V~4.3V, charge and discharge
Electric multiplying power is 0.1C, 0.2C, 0.5C, 1.0C, 2.0C, 5.0C each 5 times, is finally circulated 5 times under 0.1C.Cycle performance
The voltage range of test is also 2.6V~4.3V, is circulated 100 times under 0.5C.Electro-chemical test 0.5C discharge capacities first
For 169.8 mAh/g.
Comparative example 1
Nickel sulfate, cobaltous sulfate and manganese sulfate are made into mixed solution according to Ni:Co :Mn mol ratios are 0.5:0.2:0.3 mixing
Uniformly, the total mole number of tri- kinds of transition metal ions of Ni, Co, Mn is 2mol/L, then by 4mol/L NaOH solution
It is added to simultaneously in reaction vessel with transition metal ion solution and 4mol/L ammoniacal liquor, the pH values for controlling reaction system are
11.5, reaction temperature is 60 DEG C, and the control reaction time causes the Ni of generation0.5Co0.2Mn0.3(OH)2Particle diameter D50 be 3.5 μ
M, particle diameter distribution meet normal distribution.Then by after the filtering of obtained precipitation, washing, dried 12 hours at 120 DEG C.Will
Lithium carbonate and Ni0.5Co0.2Mn0.3(OH)2According to Li/X=1.05 (X=Ni0.5Co0.2Mn0.3(OH)2) ratio mixed
Close, after being well mixed, 800 DEG C of calcining 12h in Muffle furnace, atmosphere is 3L/min oxygen, material furnace cooling, is crushed
300 mesh sieves are crossed afterwards.
According to mass ratio it is the ︰ of 9.2 ︰, 0.3 ︰ 0.2 by [M1] positive electrode of above-mentioned synthesis, acetylene black, KS-6, PVDF
0.3 ratio is well mixed, and adds appropriate NMP, and uniform slurry is made in stirring；Slurry is uniformly applied on aluminium foil,
After being put into air dry oven drying, place into 120 DEG C of vacuum drying chamber and be dried in vacuo 12 hours；Punching is used after natural cooling
Machine goes out a diameter of 16mm disk, and disk is placed on tablet press machine with obtaining positive plate after 10MPa pressure compaction.
Using homemade positive plate as positive pole, lithium piece is negative pole, and Celgard2400 microporous polypropylene membranes are barrier film, 1mol/L's
LiPF6/EC+DMC(v:V=1:1) it is electrolyte, is all full of argon gas in below 0.1ppm in water content and oxygen content
Gloves phase in be assembled into CR2016 type experimental cells.
Carry out constant current charge-discharge test at room temperature, the test voltage scope of high rate performance is 2.6V~4.3V, charge and discharge
Electric multiplying power is 0.1C, 0.2C, 0.5C, 1.0C, 2.0C, 5.0C each 5 times, is finally circulated 5 times under 0.1C.Cycle performance
The voltage range of test is also 2.6V~4.3V, is circulated 100 times under 0.5C.
Comparative example 2
The 1mg/ml NH4VO3 aqueous solution is configured, by the NCM and NH of comparative example 14VO3Solution mixes, under the conditions of 80 DEG C constantly
Stirring evaporative removal obtains NH4VO3NCM is coated, alum acid ammonium content is 0.01-5%, afterwards by NH4VO3NCM is coated in Muffle furnace
In 600 DEG C roasting 3h obtain V2O5Coat NCM.
VO-NCM, acetylene black, KS-6, PVDF are well mixed according to the ratio that mass ratio is the ︰ 0.3 of 9.2 ︰, 0.3 ︰ 0.2,
Appropriate NMP is added, uniform slurry is made in stirring；Slurry is uniformly applied on aluminium foil, is put into air dry oven drying
Afterwards, 120 DEG C of vacuum drying chamber is placed into be dried in vacuo 12 hours；After natural cooling a diameter of 16mm is gone out with sheet-punching machine
Disk, disk is placed on tablet press machine with obtaining positive plate after 10MPa pressure compaction.Using homemade positive plate as just
Pole, lithium piece are negative pole, and Celgard2400 microporous polypropylene membranes are barrier film, 1mol/L LiPF6/EC+DMC (v:V=1:
1) it is electrolyte, CR2016 is assembled into the gloves phase full of argon gas of water content and oxygen content all in below 0.1ppm
Type experimental cell.
Carry out constant current charge-discharge test at room temperature, the test voltage scope of high rate performance is 2.6V~4.3V, charge and discharge
Electric multiplying power is 0.1C, 0.2C, 0.5C, 1.0C, 2.0C, 5.0C each 5 times, is finally circulated 5 times under 0.1C.Cycle performance
The voltage range of test is also 2.6V~4.3V, is circulated 100 times under 0.5C.
Comparative example 3
NCM, butyl thiophene (3BT) and paratoluenesulfonic acid sodium salt are uniformly mixed in absolute ethyl alcohol, FeCl3 as oxidant not
Disconnected to instill in mixture, mixture is stirred continuously 24h under the conditions of ice-water bath and carries out polymerisation.Reaction product filtering afterwards,
Wash and be dried in vacuo 12h at 80 DEG C, obtain P3BT-NCM.
P3BT-NCM, acetylene black, KS-6, PVDF are mixed according to the ratio that mass ratio is the ︰ 0.3 of 9.2 ︰, 0.3 ︰ 0.2
It is even, appropriate NMP is added, uniform slurry is made in stirring；Slurry is uniformly applied on aluminium foil, is put into air dry oven baking
After dry, place into 120 DEG C of vacuum drying chamber and be dried in vacuo 12 hours；After natural cooling a diameter of 16mm is gone out with sheet-punching machine
Disk, disk is placed on tablet press machine with obtaining positive plate after 10MPa pressure compaction.Using homemade positive plate as just
Pole, lithium piece are negative pole, and Celgard2400 microporous polypropylene membranes are barrier film, 1mol/L LiPF6/EC+DMC (v:V=1:
1) it is electrolyte, CR2016 is assembled into the gloves phase full of argon gas of water content and oxygen content all in below 0.1ppm
Type experimental cell.
Carry out constant current charge-discharge test at room temperature, the test voltage scope of high rate performance is 2.6V~4.3V, charge and discharge
Electric multiplying power is 0.1C, 0.2C, 0.5C, 1.0C, 2.0C, 5.0C each 5 times, is finally circulated 5 times under 0.1C.Cycle performance
The voltage range of test is also 2.6V~4.3V, is circulated 100 times under 0.5C.
V in NCM, comparative example 2 in comparative example 12O5Coat P3BT in NCM, comparative example 3 and coat P3BT and V in NCM embodiments 12O5
Double-coating NCM XRD is not as shown in figure 1, double-coating changes the phase structure of NCM materials.
V in NCM, comparative example 2 in comparative example 12O5Coat NCM, in comparative example 3 in P3BT cladding NCM embodiments 1 P3BT and
V2O5As shown in Figure 3 and Figure 4, NCM's high rate performance and cycle performance of double-coating NCM half-cells discharges specific volume first in 0.5C
Measure as 168.3mAh/g, V2O5In 0.5C, discharge capacity is 167.0 mAh/g to cladding NCM first, and it is first in 0.5C that P3BT coats NCM
Secondary discharge capacity is 171.3 mAh/g, P3BT and V2O5In 0.5C, discharge capacity is 170.1 mAh/g to double-coating NCM first,
Under 100 cycle-indexes, double-coating NCM stability is best, and capability retention is up to 96.0%.Conducting high polymers thing
Cladding improves the high rate performance of material, particularly becomes apparent under conditions of high current.
V in NCM, comparative example 2 in comparative example 12O5Coat NCM, in comparative example 3 in P3BT cladding NCM embodiments 1 P3BT and
V2O5Double-coating NCM half-cells 100 are charged to after circulating takes off the differential thermometric analysis figures of lithium NCM materials after 4.3V as figure 5 illustrates,
For NCM in 271 DEG C of presence, one exothermic peak, reaction heat is 601.9J g-1.V2O5 claddings NCM exothermic peak is at 284.0 DEG C, instead
It is 391.0 J g-1 to answer heat.For P3BT and V2O5 double-coatings NCM exothermic peak at 288.5 DEG C, reaction heat is 345.1 J g-1,
Illustrate that double-coating NCM materials have more preferable heat endurance.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the scope of the invention, it is every at this
Under the inventive concept of invention, the equivalent structure transformation made using description of the invention and accompanying drawing content, or directly/use indirectly
It is included in other related technical areas in the scope of patent protection of the present invention.
Claims (4)
1. a kind of nickel-cobalt lithium manganate cathode material of high security double-coating, kernel is nickle cobalt lithium manganate, it is characterised in that also
Including：Internal layer covering material V2O5, external sheath material is conductive polymer polymer.
2. the nickel-cobalt lithium manganate cathode material of high security double-coating according to claim 1, it is characterised in that described
Conductive polymer polymer is any in polypyrrole, poly- 3,4- ethene dioxythiophenes, poly- butyl thiophene, poly- 3- hexyl thiophenes
It is a kind of.
3. the nickel-cobalt lithium manganate cathode material of high security double-coating according to claim 1, it is characterised in that internal layer
Cladding thickness is 0.01-30nm, and external sheath thickness is 5-300nm.
4. the preparation side of the nickel-cobalt lithium manganate cathode material of the high security double-coating according to claim any one of 1-3
Method, it is characterised in that comprise the steps of：
（a）The preparation of kernel nickle cobalt lithium manganate particle
Nickel sulfate, cobaltous sulfate and manganese sulfate are made into mixed solution according to Ni:Co:Mn mol ratios are 0.5:0.2:0.3 mixing is equal
Even, the total mole number of tri- kinds of transition metal ions of Ni, Co, Mn is 2mol/L, then by 4mol/L NaOH solution and
Transition metal ion solution and 4mol/L ammoniacal liquor are added in reaction vessel simultaneously, and the pH values for controlling reaction system are
11.5, reaction temperature is 60 DEG C, and the control reaction time causes the Ni of generation0.5Co0.2Mn0.3(OH)2Particle diameter D50 be 3.5 μ
M, particle diameter distribution meet normal distribution；Then by after the filtering of obtained precipitation, washing, dried 12 hours at 120 DEG C；
By lithium carbonate and Ni0.5Co0.2Mn0.3(OH)2According to Li/X=1.05 (X=Ni0.5Co0.2Mn0.3(OH)2 ) ratio
Mixed, after being well mixed, 800 DEG C of calcining 12h, atmosphere are 3L/min oxygen in Muffle furnace, and material is cold with stove
But, 300 mesh sieves are crossed after crushing；
（b）Internal layer coats V2O5
Configure 1mg/ml NH4VO3The aqueous solution, by step（a）NCM and NH4VO3Solution mixes, and is constantly stirred under the conditions of 80 DEG C
Mix evaporative removal and obtain NH4VO3NCM is coated, alum acid ammonium content is 0.01-5%, afterwards by NH4VO3NCM is coated in Muffle furnace
600 DEG C of roasting 3h obtain V2O5Coat NCM；
（c）External sheath conductive polymer polymer
V2O5Cladding NCM, conducting polymer monomer and paratoluenesulfonic acid sodium salt are uniformly mixed in absolute ethyl alcohol, FeCl3As
Oxidant is constantly instilled in mixture, and mixture is stirred continuously 24h under the conditions of ice-water bath and carries out polymerisation；React afterwards
Product filtering, washing are simultaneously dried in vacuo 12h at 80 DEG C, obtain conducting polymer-VO-NCM.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108598436A (en) * | 2018-05-03 | 2018-09-28 | 中南大学 | The positive electrode and preparation method thereof that conducting polymer and manganese dioxide coat altogether |
| CN108807886A (en) * | 2018-05-31 | 2018-11-13 | 电子科技大学 | Double-coating anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2And preparation method thereof |
| CN110518200A (en) * | 2019-08-01 | 2019-11-29 | 乳源东阳光磁性材料有限公司 | A kind of carbon/iron manganese phosphate for lithium fiber filament, nickel cobalt aluminium positive electrode of praseodymium oxide double-coating and preparation method thereof |
| CN111640928A (en) * | 2020-06-30 | 2020-09-08 | 蜂巢能源科技有限公司 | NCMA quaternary system material, preparation method thereof, lithium battery positive electrode material and lithium battery |
| CN112599779A (en) * | 2020-12-15 | 2021-04-02 | 上海华谊（集团）公司 | Double-layer coated lithium ion battery anode material and preparation method thereof |
| CN113140715A (en) * | 2021-04-12 | 2021-07-20 | 广东佳纳能源科技有限公司 | Composite cathode material, preparation method thereof and lithium ion battery |
| CN113968593A (en) * | 2021-09-30 | 2022-01-25 | 广东邦普循环科技有限公司 | Method for recovering and treating ternary material micro powder and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102637871A (en) * | 2012-04-19 | 2012-08-15 | 中南大学 | Preparation method of lithium ion anode material coated with lithium ion activating oxide V2O5 |
| US20140193708A1 (en) * | 2013-01-04 | 2014-07-10 | Samsung Sdi Co., Ltd. | Positive active material composition for rechargeable lithium battery, positive electrode prepared from composition, and rechargeable lithium battery including positive electrode |
| CN104332619A (en) * | 2014-09-22 | 2015-02-04 | 上海中聚佳华电池科技有限公司 | Polypyrrole- coated full-gradient cathode material and preparation method thereof |
-
2017
- 2017-07-26 CN CN201710616454.5A patent/CN107394166A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102637871A (en) * | 2012-04-19 | 2012-08-15 | 中南大学 | Preparation method of lithium ion anode material coated with lithium ion activating oxide V2O5 |
| US20140193708A1 (en) * | 2013-01-04 | 2014-07-10 | Samsung Sdi Co., Ltd. | Positive active material composition for rechargeable lithium battery, positive electrode prepared from composition, and rechargeable lithium battery including positive electrode |
| CN104332619A (en) * | 2014-09-22 | 2015-02-04 | 上海中聚佳华电池科技有限公司 | Polypyrrole- coated full-gradient cathode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| BENBIN LUO ET AL.: ""Improved electrochemical performance of LiNi0.5Co0.2Mn0.3O2 cathode material by double-layer coating with graphene oxide and V2O5 for lithium-ion batteries"", 《APPLIED SURFACE SCIENCE》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108598436A (en) * | 2018-05-03 | 2018-09-28 | 中南大学 | The positive electrode and preparation method thereof that conducting polymer and manganese dioxide coat altogether |
| CN108807886A (en) * | 2018-05-31 | 2018-11-13 | 电子科技大学 | Double-coating anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2And preparation method thereof |
| CN110518200A (en) * | 2019-08-01 | 2019-11-29 | 乳源东阳光磁性材料有限公司 | A kind of carbon/iron manganese phosphate for lithium fiber filament, nickel cobalt aluminium positive electrode of praseodymium oxide double-coating and preparation method thereof |
| CN110518200B (en) * | 2019-08-01 | 2021-12-28 | 乳源东阳光磁性材料有限公司 | Carbon/lithium iron manganese phosphate fiber and praseodymium oxide double-layer coated nickel-cobalt-aluminum positive electrode material and preparation method thereof |
| CN111640928A (en) * | 2020-06-30 | 2020-09-08 | 蜂巢能源科技有限公司 | NCMA quaternary system material, preparation method thereof, lithium battery positive electrode material and lithium battery |
| CN112599779A (en) * | 2020-12-15 | 2021-04-02 | 上海华谊（集团）公司 | Double-layer coated lithium ion battery anode material and preparation method thereof |
| CN113140715A (en) * | 2021-04-12 | 2021-07-20 | 广东佳纳能源科技有限公司 | Composite cathode material, preparation method thereof and lithium ion battery |
| CN113140715B (en) * | 2021-04-12 | 2022-08-26 | 广东佳纳能源科技有限公司 | Composite cathode material, preparation method thereof and lithium ion battery |
| CN113968593A (en) * | 2021-09-30 | 2022-01-25 | 广东邦普循环科技有限公司 | Method for recovering and treating ternary material micro powder and application thereof |
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