CN106058214B - A kind of graphene interts the preparation method of manganese base layer structure anode material of lithium battery - Google Patents
A kind of graphene interts the preparation method of manganese base layer structure anode material of lithium battery Download PDFInfo
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- H01M4/00—Electrodes
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- 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
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention discloses the preparation methods that a kind of graphene interts manganese base layer structure anode material of lithium battery, belong to anode material of lithium battery preparation technical field.The present invention mixes graphite powder and concentrated sulfuric acid etc., it filters and pre-oxidation graphite powder is made, it is stirred to react again with concentrated sulfuric acid solution, hydrogenperoxide steam generator, hydrochloric acid etc., it is centrifuged to obtain precipitating, with burnt manganese dioxide after drying, monohydrate lithium hydroxide, the mixing and ball millings such as vulcanized sodium obtain ball milling material, deionized water is added and carries out hydro-thermal reaction, graphene is made after reactant washing is dry and interts manganese base layer structure anode material of lithium battery.The beneficial effects of the invention are as follows：Preparation step of the present invention is simple, and low energy consumption, and the period is short；Products obtained therefrom cryogenic property and good conductivity, tap density is up to 1.9~2.5g/mL.
Description
Technical field
The present invention relates to the preparation methods that a kind of graphene interts manganese base layer structure anode material of lithium battery, belong to lithium electricity
Pond positive electrode preparation technical field.
Background technique
The various electric devices of mankind's daily use, such as electric car, portable electronic product are both needed to using chemistry
Power supply.In electrochmical power source used, lithium ion battery has operating voltage height, light weight, small in size, high-energy-density, memoryless
The features such as effect, self discharge be smaller, long circulation life and be used widely, the sixth of the twelve Earthly Branches is answered extensively in portable electronic product
With, and gradually it is generalized to electric tool and electric vehicle.The performance of lithium ion battery depends primarily on its positive electrode
Performance.LiCo02（Cobalt acid lithium）It is the lithium ion battery of first generation positive electrode, but cobalt resource is limited and to environment nocuousness, cobalt
Sour lithium price is higher, and thermal stability and security performance are poor, is unsuitable for the application field of power battery.It has found later with Han
The phosphate of olive stone structure, LiFePO4 (LiFeP04), have safety more better than cobalt acid lithium, especially high temperature resistant, overcharging resisting
Electrical property is far more than cobalt acid lithium.It is increasingly becoming the dynamic lithium battery positive electrode of current main-stream.But LiFePO4 discharge potential
It is low, energy density is smaller, synthetic technological condition is more harsh, the higher Fe in preparation of industrial production cost2+It is oxidizable at Fe3 +, it is difficult to obtain single-phase LiFePO4, purity is low, and preparation process is complicated, needs long-time high-temperature calcination, and energy consumption is high, the period is long.
Although improving ion and electronic conductivity by the doping of lithium position, iron position, have by the partial size and pattern control that improve particle
Validity response area increases electron conduction etc. to improve the cryogenic property of LiFePO4, still by the way that additional conductive agent is added
The inherent characteristics of LiFePO 4 material, cryogenic property and electric conductivity are poor, and the more low factor of tap density limits it extensively
Using.
Summary of the invention
The technical problems to be solved by the invention：It is poor for current anode material of lithium battery cryogenic property and electric conductivity,
The lower drawback of tap density provides a kind of graphite powder and the concentrated sulfuric acid etc. and mixes, and filters and pre-oxidation graphite powder is made, then with it is dense
Sulfuric acid solution, hydrogenperoxide steam generator, hydrochloric acid etc. are stirred to react, and are centrifuged to obtain precipitating, it is dry after with burnt manganese dioxide, Dan Shui
Lithium hydroxide, the mixing and ball millings such as vulcanized sodium obtain ball milling material, and deionized water is added and carries out hydro-thermal reaction, makes after reactant washing is dry
Obtain the method that graphene interts manganese base layer structure anode material of lithium battery.Preparation step of the present invention is simple, short preparation period, institute
Product low temperature performance and good conductivity are obtained, tap density is high.
In order to solve the above technical problems, the present invention is using technical solution as described below：
（1）Measuring 33~35mL mass fraction is that 98% sulfuric acid solution is separately added into 5.0 under 75~80 DEG C of waters bath with thermostatic control
~6.0g graphite powder, 6.2~7.0g potassium peroxydisulfate, 6.2~7.0g phosphorus pentoxide stir 4~5h with 200~300r/min,
Mixed liquor is obtained, mixed liquor is added in 2~3L deionized water, and it is filtered with the aperture 200~300nm ultrafiltration membrane, is obtained
Filter cake after being washed with deionized filter cake 3~5 times, by filter cake natural air drying, obtains pre-oxidation graphite powder；
（2）Measuring 30~40mL mass fraction is that 98% sulfuric acid solution is separately added into 5 into sulfuric acid solution under ice-water bath
The above-mentioned pre-oxidation graphite powder of~6g, 3~4g potassium permanganate stir 15~20min with 100~200r/min, it is again heated to 35~
40 DEG C, after continuing 2~3h of stirring, stirring mixture is added in 60~70mL deionized water, 2~3h is stirred, is cooled to room temperature,
180~200mL deionized water is added, after mixing evenly, adding 5~6mL mass fraction is 30% hydrogenperoxide steam generator, wait drip
After adding 25~30min, addition 10~12mL mass fraction is 37% hydrochloric acid, continues 1~2h of stirring, stands 20~for 24 hours, be transferred to from
In scheming, 10~15min is centrifugated with 5000~6000r/min, collects precipitating, and precipitating 3~5 is washed with deionized
It is secondary, precipitating is placed in 60~70 DEG C of drying boxes dry 3~4h, obtains graphene oxide sheet；
（3）It weighs 8.7~13.1g manganese dioxide to be placed in tube furnace, at 800~850 DEG C, 10~12h is calcined, with furnace
After being cooled to room temperature, take out, by its respectively with 16.8~20.2g monohydrate lithium hydroxide, 1.6~1.9g vulcanized sodium, 1.5~2.0g
Above-mentioned graphene oxide sheet mixing, is fitted into ball grinder, while 20~30mL dehydrated alcohol being added into filling, with 120~150r/
Min 3~4h of ball milling, natural air drying obtain ball milling material；
（4）The above-mentioned ball milling material of 5~6g is weighed, is added in 60~72mL deionized water, is stirred with 300~400r/min
After 1~2h, it is packed into reaction kettle, is placed in hydro-thermal reaction 20 in 180~200 DEG C of air dry ovens~for 24 hours, takes out reactant, and
Reactant to cleaning solution is washed with deionized to be in neutrality, the reactant after washing is placed in 80~90 DEG C of air dry ovens and is done
Dry 2~3h obtains graphene and interts manganese base layer structure anode material of lithium battery.
Application method of the invention：By graphene produced by the present invention intert manganese base layer structure anode material of lithium battery,
Kynoar, acetylene black in mass ratio 8:1:1 is mixed, and mixture quality 1~2%N- methyl pyrrolidone is added,
It is ground into paste in agate mortar, is applied on aluminium foil, dries 10~12h in air atmosphere, then is dry in 70~80 DEG C of vacuum
Dry 10~12h in dry case, it is 8~10mm pole piece that diameter, which is made, is put into the glove box full of argon gas and is made into battery.It should
Material tap density is up to 1.9~2.5g/mL, in 10C discharge capacity up to 131~136mAh-1, under 0.5C, follow for 80~90 times
Its discharge capacitance is 99.4% or more after ring, and low temperature performance well is worthy to be popularized and uses.
The present invention is compared with other methods, and advantageous effects are：
（1）Preparation step of the present invention is simple, and low energy consumption, and the period is short；
（2）Products obtained therefrom cryogenic property and good conductivity, tap density is up to 1.9~2.5g/mL.
Specific embodiment
Measuring 33~35mL mass fraction first is that 98% sulfuric acid solution is separately added under 75~80 DEG C of waters bath with thermostatic control
5.0~6.0g graphite powder, 6.2~7.0g potassium peroxydisulfate, 6.2~7.0g phosphorus pentoxide, with 200~300r/min stirring 4~
5h obtains mixed liquor, and mixed liquor is added in 2~3L deionized water, and is filtered with the aperture 200~300nm ultrafiltration membrane to it,
Filter cake is obtained, after being washed with deionized filter cake 3~5 times, by filter cake natural air drying, obtains pre-oxidation graphite powder；Measure 30 again~
40mL mass fraction is that 98% sulfuric acid solution is separately added into the above-mentioned pre-oxidation graphite of 5~6g into sulfuric acid solution under ice-water bath
Powder, 3~4g potassium permanganate stir 15~20min with 100~200r/min, are again heated to 35~40 DEG C, continue 2~3h of stirring
Afterwards, will stirring mixture be added 60~70mL deionized water in, stir 2~3h, be cooled to room temperature, be added 180~200mL go from
Sub- water, after mixing evenly, adding 5~6mL mass fraction is 30% hydrogenperoxide steam generator, after 25~30min is added dropwise, is added
10~12mL mass fraction is 37% hydrochloric acid, continues 1~2h of stirring, stands 20~for 24 hours, is transferred in centrifuge, with 5000~
6000r/min is centrifugated 10~15min, collects precipitating, and is washed with deionized precipitating 3~5 times, precipitating is placed in 60~
Dry 3~4h, obtains graphene oxide sheet in 70 DEG C of drying boxes；Then 8.7~13.1g manganese dioxide is weighed to be placed in tube furnace,
At 800~850 DEG C, calcine 10~12h, after cooling to room temperature with the furnace, take out, by its respectively with the mono- water hydrogen of 16.8~20.2g
The above-mentioned graphene oxide sheet mixing of lithia, 1.6~1.9g vulcanized sodium, 1.5~2.0g, is fitted into ball grinder, while into filling
20~30mL dehydrated alcohol is added, with 120~150r/min, 3~4h of ball milling, natural air drying obtains ball milling material；Finally weigh 5~6g
Above-mentioned ball milling material is added in 60~72mL deionized water, after being stirred 1~2h with 300~400r/min, is packed into reaction kettle,
It is placed in hydro-thermal reaction 20 in 180~200 DEG C of air dry ovens~for 24 hours, takes out reactant, and reactant is washed with deionized
It is in neutrality to cleaning solution, the reactant after washing is placed in 80~90 DEG C of air dry ovens dry 2~3h, it is interspersed to obtain graphene
Manganese base layer structure anode material of lithium battery.
Example 1
Measuring 33mL mass fraction first is that 98% sulfuric acid solution is separately added into 5.0g graphite under 75 DEG C of waters bath with thermostatic control
Powder, 6.2g potassium peroxydisulfate, 6.2g phosphorus pentoxide, stir 4h with 200r/min, obtain mixed liquor, and 2L deionization is added in mixed liquor
In water, and it is filtered with the aperture 200nm ultrafiltration membrane, obtain filter cake, after being washed with deionized filter cake 3 times, certainly by filter cake
It so air-dries, obtains pre-oxidation graphite powder；Measuring 30mL mass fraction again is 98% sulfuric acid solution, under ice-water bath, into sulfuric acid solution
It is separately added into the above-mentioned pre-oxidation graphite powder of 5g, 3g potassium permanganate stirs 15min with 100r/min, is again heated to 35 DEG C, continues to stir
After mixing 2h, stirring mixture is added in 60mL deionized water, 2h is stirred, is cooled to room temperature, 180mL deionized water is added, stirs
After mixing uniformly, adding 5mL mass fraction is 30% hydrogenperoxide steam generator, and after 25~30min is added dropwise, 10mL mass point is added
Number is 37% hydrochloric acid, continues to stir 1h, stands 20h, be transferred in centrifuge, is centrifugated 10min with 5000r/min, and it is heavy to collect
It forms sediment, and precipitating is washed with deionized 3 times, precipitating is placed in 60 DEG C of drying boxes dry 3h, obtains graphene oxide sheet；Then claim
Take 8.7g manganese dioxide to be placed in tube furnace, at 800 DEG C, calcine 10h, after cooling to room temperature with the furnace, take out, by its respectively with
The above-mentioned graphene oxide sheet mixing of 16.8g monohydrate lithium hydroxide, 1.6g vulcanized sodium, 1.5g, is fitted into ball grinder, while into filling
20mL dehydrated alcohol is added, with 120r/min ball milling 3h, natural air drying obtains ball milling material；The above-mentioned ball milling material of 5g is finally weighed, is added
In 60mL deionized water, after being stirred 1h with 300r/min, it is packed into reaction kettle, is placed in hydro-thermal in 180 DEG C of air dry ovens
20h is reacted, reactant is taken out, and reactant to cleaning solution is washed with deionized and is in neutrality, the reactant after washing is placed in
Dry 2h in 80 DEG C of air dry ovens, obtains graphene and interts manganese base layer structure anode material of lithium battery.
Application method of the invention is：Graphene produced by the present invention is interted into manganese base layer structure lithium battery anode material
Material, Kynoar, acetylene black in mass ratio 8:1:1 is mixed, and mixture quality 1%N- methyl pyrrolidone is added,
It is ground into paste in agate mortar, is applied on aluminium foil, dries 10h in air atmosphere, then is done in 70 DEG C of vacuum ovens
Dry 10h, it is 8mm pole piece that diameter, which is made, is put into the glove box full of argon gas and is made into battery.The material tap density reaches
1.9g/mL reaches 131mAh in 10C discharge capacity-1, under 0.5C, its discharge capacitance is 99.48% after 80 circulations,
Low temperature performance well is worthy to be popularized and uses.
Example 2
Measuring 34mL mass fraction first is that 98% sulfuric acid solution is separately added into 5.5g graphite under 78 DEG C of waters bath with thermostatic control
Powder, 6.6g potassium peroxydisulfate, 6.6g phosphorus pentoxide, stir 5h with 250r/min, obtain mixed liquor, and 3L deionization is added in mixed liquor
In water, and it is filtered with the aperture 250nm ultrafiltration membrane, obtain filter cake, after being washed with deionized filter cake 4 times, certainly by filter cake
It so air-dries, obtains pre-oxidation graphite powder；Measuring 35mL mass fraction again is 98% sulfuric acid solution, under ice-water bath, into sulfuric acid solution
It is separately added into the above-mentioned pre-oxidation graphite powder of 6g, 4g potassium permanganate stirs 18min with 150r/min, is again heated to 38 DEG C, continues to stir
After mixing 3h, stirring mixture is added in 65mL deionized water, 3h is stirred, is cooled to room temperature, 190mL deionized water is added, stirs
After mixing uniformly, adding 6mL mass fraction is 30% hydrogenperoxide steam generator, and after 25~30min is added dropwise, 11mL mass point is added
Number is 37% hydrochloric acid, continues to stir 2h, stands 22h, be transferred in centrifuge, is centrifugated 13min with 5500r/min, and it is heavy to collect
It forms sediment, and precipitating is washed with deionized 4 times, precipitating is placed in 65 DEG C of drying boxes dry 4h, obtains graphene oxide sheet；Then claim
It takes 11.0g manganese dioxide to be placed in tube furnace, at 825 DEG C, calcines 11h, after cooling to room temperature with the furnace, take out, distinguished
It mixes, is fitted into ball grinder with 18.5g monohydrate lithium hydroxide, 1.7g vulcanized sodium, the above-mentioned graphene oxide sheet of 1.8g, while to filling
Middle addition 25mL dehydrated alcohol, with 135r/min ball milling 4h, natural air drying obtains ball milling material；The above-mentioned ball milling material of 6g is finally weighed, is added
Enter in 66mL deionized water, after being stirred 2h with 350r/min, is packed into reaction kettle, is placed in water in 190 DEG C of air dry ovens
Thermal response 22h takes out reactant, and reactant to cleaning solution is washed with deionized and is in neutrality, and the reactant after washing is set
The dry 3h in 85 DEG C of air dry ovens, obtains graphene and interts manganese base layer structure anode material of lithium battery.
Graphene produced by the present invention is interted into manganese base layer structure anode material of lithium battery, Kynoar, acetylene black
In mass ratio 8:1:1 is mixed, and is added mixture quality 2%N- methyl pyrrolidone, is ground into paste in the agate mortar
Object is applied on aluminium foil, dries 11h in air atmosphere, then the dry 11h in 75 DEG C of vacuum ovens, and it is the pole 9mm that diameter, which is made,
Piece is put into the glove box full of argon gas and is made into battery.The material tap density reaches 2.3g/mL, in 10C discharge capacity
Up to 134mAh-1, under 0.5C, its discharge capacitance is 99.56% after 85 circulations, and low temperature performance well is worthy to be popularized and makes
With.
Example 3
Measuring 35mL mass fraction first is that 98% sulfuric acid solution is separately added into 6.0g graphite under 80 DEG C of waters bath with thermostatic control
Powder, 7.0g potassium peroxydisulfate, 7.0g phosphorus pentoxide, stir 5h with 300r/min, obtain mixed liquor, and 3L deionization is added in mixed liquor
In water, and it is filtered with the aperture 300nm ultrafiltration membrane, obtain filter cake, after being washed with deionized filter cake 5 times, certainly by filter cake
It so air-dries, obtains pre-oxidation graphite powder；Measuring 40mL mass fraction again is 98% sulfuric acid solution, under ice-water bath, into sulfuric acid solution
It is separately added into the above-mentioned pre-oxidation graphite powder of 6g, 4g potassium permanganate stirs 20min with 200r/min, is again heated to 40 DEG C, continues to stir
After mixing 3h, stirring mixture is added in 70mL deionized water, 3h is stirred, is cooled to room temperature, 200mL deionized water is added, stirs
After mixing uniformly, adding 6mL mass fraction is 30% hydrogenperoxide steam generator, and after 25~30min is added dropwise, 12mL mass point is added
Number is 37% hydrochloric acid, continues to stir 2h, stands for 24 hours, be transferred in centrifuge, is centrifugated 15min with 6000r/min, and it is heavy to collect
It forms sediment, and precipitating is washed with deionized 5 times, precipitating is placed in 70 DEG C of drying boxes dry 4h, obtains graphene oxide sheet；Then claim
It takes 13.1g manganese dioxide to be placed in tube furnace, at 850 DEG C, calcines 12h, after cooling to room temperature with the furnace, take out, distinguished
It mixes, is fitted into ball grinder with 20.2g monohydrate lithium hydroxide, 1.9g vulcanized sodium, the above-mentioned graphene oxide sheet of 2.0g, while to filling
Middle addition 30mL dehydrated alcohol, with 150r/min ball milling 4h, natural air drying obtains ball milling material；The above-mentioned ball milling material of 6g is finally weighed, is added
Enter in 72mL deionized water, after being stirred 2h with 400r/min, is packed into reaction kettle, is placed in water in 200 DEG C of air dry ovens
Thermal response for 24 hours, takes out reactant, and reactant to cleaning solution is washed with deionized and is in neutrality, the reactant after washing is set
The dry 3h in 90 DEG C of air dry ovens, obtains graphene and interts manganese base layer structure anode material of lithium battery.
Graphene produced by the present invention is interted into manganese base layer structure anode material of lithium battery, Kynoar, acetylene black
In mass ratio 8:1:1 is mixed, and is added mixture quality 2%N- methyl pyrrolidone, is ground into paste in the agate mortar
Object is applied on aluminium foil, dries 12h in air atmosphere, then the dry 12h in 80 DEG C of vacuum ovens, and it is 10mm that diameter, which is made,
Pole piece is put into the glove box full of argon gas and is made into battery.The material tap density reaches 2.5g/mL, transfers capacitor in 10C
Amount reaches 136mAh-1, under 0.5C, its discharge capacitance is 99.72% after 90 circulations, low temperature performance well, be worthy to be popularized with
It uses.
Claims (1)
1. the preparation method that a kind of graphene interts manganese base layer structure anode material of lithium battery, it is characterised in that specific preparation step
Suddenly it is：
（1）Measurement 33~35mL mass fraction is 98% sulfuric acid solution, under 75~80 DEG C of waters bath with thermostatic control, it is separately added into 5.0~
6.0g graphite powder, 6.2~7.0g potassium peroxydisulfate, 6.2~7.0g phosphorus pentoxide stir 4~5h with 200~300r/min, obtain
Mixed liquor is added in 2~3L deionized water, and is filtered with the aperture 200~300nm ultrafiltration membrane to it by mixed liquor, must filter
Cake after being washed with deionized filter cake 3~5 times, by filter cake natural air drying, obtains pre-oxidation graphite powder；
（2）Measuring 30~40mL mass fraction is that 98% sulfuric acid solution is separately added into 5~6g into sulfuric acid solution under ice-water bath
Above-mentioned pre-oxidation graphite powder, 3~4g potassium permanganate stir 15~20min with 100~200r/min, are again heated to 35~40 DEG C,
After continuing 2~3h of stirring, stirring mixture is added in 60~70mL deionized water, 2~3h is stirred, is cooled to room temperature, is added
180~200mL deionized water, after mixing evenly, adding 5~6mL mass fraction is 30% hydrogenperoxide steam generator, wait be added dropwise 25
After~30min, addition 10~12mL mass fraction is 37% hydrochloric acid, continues 1~2h of stirring, stand 20~for 24 hours, it is transferred to centrifuge
In, 10~15min is centrifugated with 5000~6000r/min, collects precipitating, and be washed with deionized precipitating 3~5 times, it will
Precipitating is placed in 60~70 DEG C of drying boxes dry 3~4h, obtains graphene oxide sheet；
（3）It weighs 8.7~13.1g manganese dioxide to be placed in tube furnace, at 800~850 DEG C, calcines 10~12h, furnace cooling
To room temperature, take out, it is above-mentioned with 16.8~20.2g monohydrate lithium hydroxide, 1.6~1.9g vulcanized sodium, 1.5~2.0g respectively
Graphene oxide sheet mixing, is fitted into ball grinder, while 20~30mL dehydrated alcohol being added into filling, with 120~150r/min
3~4h of ball milling, natural air drying obtain ball milling material；
（4）It weighs the above-mentioned ball milling material of 5~6g, is added in 60~72mL deionized water, 1 is stirred with 300~400r/min~
After 2h, it is packed into reaction kettle, is placed in hydro-thermal reaction 20 in 180~200 DEG C of air dry ovens~for 24 hours, takes out reactant, and spend
Ionized water washing reaction object to cleaning solution is in neutrality, and the reactant after washing is placed in 80~90 DEG C of air dry ovens dry 2
~3h obtains graphene and interts manganese base layer structure anode material of lithium battery.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102280617A (en) * | 2011-07-06 | 2011-12-14 | 中国科学院过程工程研究所 | Carbon material modified composite lithium manganese oxide cathode material applied to lithium ion battery and preparation method thereof |
| CN104393283A (en) * | 2014-10-20 | 2015-03-04 | 中国工程物理研究院化工材料研究所 | Nano crystalline CoO-graphene composite material as well as preparation and application thereof |
| CN104868105A (en) * | 2015-04-15 | 2015-08-26 | 南京邮电大学 | Preparation method of three-dimensional graphene composite electrode material with high mechanical strength |
Family Cites Families (1)
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| JP5717867B2 (en) * | 2010-12-22 | 2015-05-13 | オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド | Electrode plate and method for preparing the same, super capacitor and lithium ion battery |
-
2016
- 2016-08-05 CN CN201610636578.5A patent/CN106058214B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102280617A (en) * | 2011-07-06 | 2011-12-14 | 中国科学院过程工程研究所 | Carbon material modified composite lithium manganese oxide cathode material applied to lithium ion battery and preparation method thereof |
| CN104393283A (en) * | 2014-10-20 | 2015-03-04 | 中国工程物理研究院化工材料研究所 | Nano crystalline CoO-graphene composite material as well as preparation and application thereof |
| CN104868105A (en) * | 2015-04-15 | 2015-08-26 | 南京邮电大学 | Preparation method of three-dimensional graphene composite electrode material with high mechanical strength |
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