CN105845462B - Preparation method based on three-dimensional grapheme/mangano-manganic oxide combination electrode material - Google Patents
Preparation method based on three-dimensional grapheme/mangano-manganic oxide combination electrode material Download PDFInfo
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Abstract
The invention discloses a kind of preparation method based on three-dimensional grapheme/mangano-manganic oxide combination electrode material.The present invention long graphene in the life of three-dimensional foam corronil first using chemical vapour deposition technique；Then corronil is removed, the three-dimensional grapheme of the self-supporting with multichannel hole is prepared；Finally, three-dimensional grapheme is immersed in the mixed solution of potassium permanganate and sodium nitrate, mangano-manganic oxide is grown on three-dimensional grapheme, three-dimensional grapheme/mangano-manganic oxide combination electrode material is prepared.The three-dimensional grapheme that this method is prepared/mangano-manganic oxide combination electrode material is multichannel hole network structure, and ion transport number of channels is more, has superhigh specific surface area, high conductivity.Available for the combination electrode for preparing super capacitor, it can also be used to prepare the combination electrode of other energy-storage travelling wave tubes.
Description
Technical field
The invention belongs to physical technology field, further relates to a kind of base in material science and electrochemical technology field
In the preparation method of three-dimensional grapheme/mangano-manganic oxide combination electrode material.The combination electrode material that the present invention is prepared can
For preparing the combination electrode of super capacitor, it can also be used to prepare the combination electrode of other energy-storage travelling wave tubes.
Background technology
Super capacitor because have the advantages that power density is high, the discharge and recharge time is short, it is pollution-free, have extended cycle life, become
A kind of novel energy-storing element.The electrode material of ultracapacitor includes carbon-based electrode material, metal oxide electrode material and led
Electric polymer electrode material.As energy problem is of increasing concern, seek it is a kind of there is high-capacitance, the short discharge and recharge time,
The electrode material of the advantages that high-specific surface area becomes the problem of anxious to be resolved.
Patent " porous-metal nickel and its base Alloy Coating On 45 oxide porous membrane super capacitor electrode material of Shenzhen University's application
A kind of porous-metal nickel is disclosed in the preparation method of material " (application number 201410605614.2, publication No. CN 104332324A)
And its preparation method of base Alloy Coating On 45 oxide porous membrane super capacitance electrode material.This method concretely comprises the following steps：(1) will
Metal is Ni-based to be used as positive pole, carries out step anodized using step anodizing is Ni-based to the metal of positive pole, is formed
Porous nickel；(2) by porous nickel in alkali lye, handled with cycle voltammetry or constant current charge-discharge method, form porous gold
Belong to nickel and its base Alloy Coating On 45 oxide porous membrane super capacitance electrode material.Although the preparation method is by two electrode DCs electricity
Source, anode is produced electroshock by step anode potential method and swing, you can realize and pore-creating is carried out to metallic nickel.But this method is still
So existing weak point is：First, this method uses step anodizing, to metallic nickel pore-creating, hole uniformity is not high, no
Beneficial to the uniform ion transport passage of formation.Second, the porous nickel that this method is prepared using step anodizing compares table
Area is not high.
The content of the invention
The purpose of the present invention is to be directed to above-mentioned problems of the prior art, proposes one kind with three-dimensional grapheme, four oxygen
Change the method that three manganese prepare the combination electrode material based on three-dimensional grapheme/mangano-manganic oxide for primary raw material.
To achieve the above object, concrete thought of the invention is：First, using chemical vapour deposition technique, in three-dimensional foam
The upper long graphene of corronil life；Then corronil is removed, the three-dimensional graphite with multichannel hole network structure is prepared
Alkene；Finally, three-dimensional grapheme is immersed in the mixed solution of potassium permanganate and sodium nitrate, four oxidations is grown on three-dimensional grapheme
Three manganese, obtain three-dimensional grapheme/mangano-manganic oxide combination electrode.
The present invention's comprises the following steps that：
(1) substrate pretreatment：
(1a) is ironed by the nickel foam that thickness is 1.6mm using press, obtains the nickel foam thin slice that thickness is 0.25mm；
After (1b) cleans nickel foam thin slice with ethanol, deionized water, 5M HCl solutions, with deionized water by nickel foam thin slice
Clean up, the nickel foam thin slice after being cleaned；
(2) electrochemically depositing copper：
Using electrochemistry three-electrode method, the nickel foam thin slice after cleaning is placed in CuSO4·5H2O and HBO3Mixed solution
In, chemical deposition voltage is powered up, is deposited 50~150 minutes, obtains covering the nickel foam thin slice of copper；
(3) high annealing：
The nickel foam thin slice for covering copper is placed in the flat-temperature zone of chemical vapor deposition CVD tube furnaces, is passed through 5sccm argon gas
With 1sccm hydrogen, 1100 DEG C of high annealing is carried out 0.5~2 hour, obtain corronil；
(4) electrochemistry selective corrosion：
Using electrochemistry three-electrode method, corronil is placed in CuSO4·5H2O and HBO3Mixed solution in, add corrosion
Voltage, corrodes three-dimensional corronil skeleton 500~1500 seconds, and the three-dimensional cupro-nickel with multichannel hole network structure is prepared and closes
Golden skeleton；
(5) three-dimensional grapheme/corronil is prepared：
(5a) uses chemical vapour deposition technique, and three-dimensional corronil skeleton is placed in into chemical vapor deposition CVD system tubular type
In the flat-temperature zone of stove, the mixed gas of 20sccm argon gas and hydrogen is passed through 5~10 minutes；
(5b) by diamond heating to 600 DEG C when, be passed through 2~20sccm ethene, keep atmosphere constant, grow 5~10
Hour；
(5c) after tubular type furnace temperature is reduced into room temperature, takes out the sample in tube furnace, obtained by the way of cooling rapidly
Three-dimensional grapheme/corronil；
(6) self-supporting three-dimensional grapheme is prepared：
Three-dimensional grapheme/corronil is placed in the mixed solution of 0.5~2M iron chloride and 1~3M hydrochloric acid, corrosion 24
Hour, obtain self-supporting three-dimensional grapheme；
(7) mangano-manganic oxide is grown：
(7a) rinses self-supporting three-dimensional grapheme with deionized water well, obtains three-dimensional grapheme；
Three-dimensional grapheme is immersed in 4M salpeter solutions 30 minutes by (7b), is cleaned up, obtained with deionized water after taking-up
Three-dimensional grapheme after to cleaning；
The mixed solution of potassium permanganate and sodium nitrate is put into autoclave by (7c), and the three-dimensional grapheme after cleaning is immersed
In the mixed solution of potassium permanganate and sodium nitrate, grow 20~30 minutes；
(7d) takes out the three-dimensional grapheme being immersed in the mixed solution of potassium permanganate and sodium nitrate, is naturally cooling to room temperature
Afterwards, dry, obtain three-dimensional grapheme/mangano-manganic oxide combination electrode.
Compared with prior art, the invention has the advantages that：
Firstth, due to the present invention using chemical vapour deposition technique prepared on three-dimensional corronil skeleton three-dimensional grapheme/
Mangano-manganic oxide combination electrode, overcoming method used in the prior art causes hole uniformity not high, is unfavorable for being formed
The deficiency of even ion transport passage so that the present invention has multiple, more uniform ion transport passage, metal oxide profit
With rate it is high the advantages of.
Secondth, because the present invention is using the three-dimensional corronil skeleton of electrochemistry three-electrode method corrosion, prior art is overcome
The not high deficiency of the middle porous nickel specific surface area that is prepared using step anodizing so that the present invention has ion transport
Number of channels is more, superhigh specific surface area, the advantages of high conductivity.
Brief description of the drawings
Fig. 1 is the flow chart of the present invention；
Fig. 2 is that the SEM SEM that mangano-manganic oxide growth time is 20 minutes in the present invention schemes；
Fig. 3 is that the SEM SEM that mangano-manganic oxide growth time is 30 minutes in the present invention schemes；
Embodiment：
In order that objects and advantages of the present invention are more clearly understood, the present invention is carried out below in conjunction with drawings and examples
It is further described.
Referring to the drawings 1, the present invention comprises the following steps that：
Step 1：Substrate pretreatment.
It is using press that the nickel foam that thickness is 1.6mm is ironed, the nickel foam thin slice that thickness is 0.25mm is obtained, then
Nickel foam thin slice is cleaned with ethanol, deionized water, 5M HCl solutions, is finally cleaned up nickel foam thin slice with deionized water,
Nickel foam thin slice after being cleaned.
Step 2：Electrochemically depositing copper.
Using electrochemistry three-electrode method, wherein working electrode is nickel foam thin slice, reference electrode Ag/AgCl, aids in electricity
Extremely Pt, the nickel foam thin slice after cleaning is placed in 0.5~3M CuSO4·5H2O and 1~2M HBO3Mixed solution in,
Add -2~-0.2V electrochemical deposition voltage, deposit 100~150 minutes, obtain covering the nickel foam thin slice of copper.
Step 3：High annealing.
The nickel foam thin slice for covering copper is placed in the flat-temperature zone of chemical vapor deposition CVD tube furnaces, is passed through 5sccm argon gas
1100 DEG C of high annealing 0.5~2 hour is carried out with 1sccm hydrogen, obtains corronil.
Step 4：Electrochemistry selective corrosion.
Using electrochemistry three-electrode method, wherein working electrode is corronil, reference electrode Ag/AgCl, auxiliary electrode
For Pt, corronil is placed in 0.5~3M CuSO4·5H2O and 1~2M HBO3Mixed solution in, add 0.2~1V corruption
Voltage is lost, corrodes three-dimensional corronil skeleton 500~1500 seconds, the three-dimensional cupro-nickel with multichannel hole network structure is prepared
Alloy skeleton.
Step 5：Prepare three-dimensional grapheme/corronil.
First, using chemical vapour deposition technique, three-dimensional corronil skeleton is placed in chemical vapor deposition CVD system tubular type
In the flat-temperature zone of stove, the mixed gas of 20sccm argon gas and hydrogen is passed through 5~10 minutes, then, by diamond heating to 600
DEG C, 2~20sccm ethene is passed through, keeps atmosphere constant, grows 5~10 hours, finally, will by the way of cooling rapidly
After tubular type furnace temperature is reduced to room temperature, the sample in tube furnace is taken out, obtains three-dimensional grapheme/corronil.
Step 6：Prepare self-supporting three-dimensional grapheme.
Three-dimensional grapheme/corronil is placed in the mixed solution of 0.5~2M iron chloride and 1~3M hydrochloric acid, solution temperature
Spend for 60~80 DEG C, corrode 24 hours, obtain self-supporting three-dimensional grapheme.
Step 7：Grow mangano-manganic oxide.
Self-supporting three-dimensional grapheme is rinsed well with deionized water, obtains three-dimensional grapheme, then, by three-dimensional grapheme
It is immersed in 4M salpeter solutions 30 minutes, it is 50~70 DEG C to keep salpeter solution temperature, finally, takes out three-dimensional grapheme and spends
Ionized water cleans up, the three-dimensional grapheme after being cleaned.
The mixed solution of potassium permanganate (0.1mol/L) and sodium nitrate (0.1mol/L) is put into autoclave, after cleaning
Three-dimensional grapheme immerse in the mixed solution of potassium permanganate and sodium nitrate, it is 150~180 DEG C to keep solution temperature, growth 20
~30 minutes.
The three-dimensional grapheme being immersed in the mixed solution of potassium permanganate and sodium nitrate is taken out, after being naturally cooling to room temperature,
Drying, obtains three-dimensional grapheme/mangano-manganic oxide combination electrode.
In order to illustrate the three-dimensional grapheme/mangano-manganic oxide combination electrode of the invention for easily preparing superhigh specific surface area,
Preparation method of the invention based on three-dimensional grapheme/mangano-manganic oxide combination electrode material, provides the following two kinds embodiment, to this
Invention is based on three-dimensional grapheme/mangano-manganic oxide combination electrode in the system that mangano-manganic oxide growth time is 20 minutes and 30 minutes
Preparation Method illustrates.Referring to the drawings 2, accompanying drawing 3, the electrochemical deposition voltage in electrochemically depositing copper is -2~-0.2V, deposition
Time is 100~150 minutes, and the corrosion potentials in electrochemistry selective corrosion are 0.2~1V, and etching time is 500~1500
Second, the annealing time in high annealing is 0.5~2 hour, prepares 0.5~2M iron chloride in three-dimensional grapheme/corronil
Temperature with the mixed solution of 1~3M hydrochloric acid is 60~80 DEG C, and the temperature for growing the 4M salpeter solutions in mangano-manganic oxide is 50
~70 DEG C, the temperature of the mixed solution of potassium permanganate and sodium nitrate is 150~180 DEG C.
Embodiment 1：Based on three-dimensional grapheme/mangano-manganic oxide combination electrode mangano-manganic oxide growth time be 20 minutes
Preparation.
Step 1：Substrate pretreatment.
It is using press that the nickel foam that thickness is 1.6mm is ironed, the nickel foam thin slice that thickness is 0.25mm is obtained, then
Nickel foam thin slice is cleaned with ethanol, deionized water, 5M HCl solutions, is finally cleaned up nickel foam thin slice with deionized water,
Nickel foam thin slice after being cleaned.
Step 2：Electrochemically depositing copper.
Using electrochemistry three-electrode method, wherein working electrode is nickel foam thin slice, reference electrode Ag/AgCl, aids in electricity
Extremely Pt, the nickel foam thin slice after cleaning is placed in 2M CuSO4·5H2O and 1M HBO3Mixed solution in, plus -0.5V
Electrochemical deposition voltage, deposit 150 minutes, obtain cover copper nickel foam thin slice.
Step 3：High annealing.
The nickel foam thin slice for covering copper is placed in the flat-temperature zone of chemical vapor deposition CVD tube furnaces, is passed through 5sccm argon gas
1100 DEG C of high annealing 1.5 hours is carried out with 1sccm hydrogen, obtains corronil.
Step 4：Electrochemistry selective corrosion.
Using electrochemistry three-electrode method, wherein working electrode is corronil, reference electrode Ag/AgCl, auxiliary electrode
For Pt, corronil is placed in 3M CuSO4·5H2O and 1.5M HBO3Mixed solution in, plus 0.2V corrosion potentials,
Corrosion 1000 seconds, is prepared the three-dimensional corronil skeleton with multichannel hole network structure.
Step 5：Prepare three-dimensional grapheme/corronil.
First, using chemical vapour deposition technique, three-dimensional corronil skeleton is placed in chemical vapor deposition CVD system tubular type
In the flat-temperature zone of stove, the mixed gas of 20sccm argon gas and hydrogen is passed through 5 minutes, then, by diamond heating to 600 DEG C, lead to
Enter 5sccm ethene, keep atmosphere constant, grow 10 hours, finally, by the way of cooling rapidly, tubular type furnace temperature is dropped
After room temperature, the sample in tube furnace is taken out, obtains three-dimensional grapheme/corronil.
Step 6：Prepare self-supporting three-dimensional grapheme.
Three-dimensional grapheme/corronil is placed in the mixed solution of 0.5M iron chloride and 1M hydrochloric acid, solution temperature 70
DEG C, corrode 24 hours, obtain self-supporting three-dimensional grapheme.
Step 7：Grow mangano-manganic oxide.
Self-supporting three-dimensional grapheme is rinsed well with deionized water, obtains three-dimensional grapheme, then, by three-dimensional grapheme
It is immersed in 4M salpeter solutions 30 minutes, it is 60 DEG C to keep salpeter solution temperature, finally, takes out three-dimensional grapheme and uses deionization
Water cleans up, the three-dimensional grapheme after being cleaned.
The mixed solution of potassium permanganate (0.1mol/L) and sodium nitrate (0.1mol/L) is put into autoclave, after cleaning
Three-dimensional grapheme immerse in the mixed solution of potassium permanganate and sodium nitrate, it is 180 DEG C to keep solution temperature, is grown 20 minutes.
The three-dimensional grapheme being immersed in the mixed solution of potassium permanganate and sodium nitrate is taken out, after being naturally cooling to room temperature,
Drying, obtains three-dimensional grapheme/mangano-manganic oxide combination electrode.
Embodiment 2：Based on three-dimensional grapheme/mangano-manganic oxide combination electrode mangano-manganic oxide growth time be 30 minutes
Preparation.
Step A：Substrate pretreatment.
It is using press that the nickel foam that thickness is 1.6mm is ironed, the nickel foam thin slice that thickness is 0.25mm is obtained, then
Nickel foam thin slice is cleaned with ethanol, deionized water, 5M HCl solutions, is finally cleaned up nickel foam thin slice with deionized water,
Nickel foam thin slice after being cleaned.
Step B：Electrochemically depositing copper.
Using electrochemistry three-electrode method, wherein working electrode is nickel foam thin slice, reference electrode Ag/AgCl, aids in electricity
Extremely Pt, the nickel foam thin slice after cleaning is placed in 2M CuSO4·5H2O and 1M HBO3Mixed solution in, plus -1V's
Electrochemical deposition voltage, deposit 100 minutes, obtain covering the nickel foam thin slice of copper.
Step C：High annealing.
The nickel foam thin slice for covering copper is placed in the flat-temperature zone of chemical vapor deposition CVD tube furnaces, is passed through 5sccm argon gas
1100 DEG C of high annealing 1 hour is carried out with 1sccm hydrogen, obtains corronil.
Step D：Electrochemistry selective corrosion.
Using electrochemistry three-electrode method, wherein working electrode is corronil, reference electrode Ag/AgCl, auxiliary electrode
For Pt, corronil is placed in 2M CuSO4·5H2O and 1M HBO3Mixed solution in, it is rotten plus 0.6V corrosion potentials
Erosion 1000 seconds, is prepared the three-dimensional corronil skeleton with multichannel hole network structure.
Step E：Prepare three-dimensional grapheme/corronil.
First, using chemical vapour deposition technique, three-dimensional corronil skeleton is placed in chemical vapor deposition CVD system tubular type
In the flat-temperature zone of stove, the mixed gas of 20sccm argon gas and hydrogen is passed through 5 minutes, then, by diamond heating to 600 DEG C, lead to
Enter 10sccm ethene, keep atmosphere constant, grow 10 hours, finally, by the way of cooling rapidly, tubular type furnace temperature is dropped
After room temperature, the sample in tube furnace is taken out, obtains three-dimensional grapheme/corronil.
Step F：Prepare self-supporting three-dimensional grapheme.
Three-dimensional grapheme/corronil being placed in the mixed solution of 1M iron chloride and 2M hydrochloric acid, solution temperature is 80 DEG C,
Corrosion 24 hours, obtains self-supporting three-dimensional grapheme.
Step G：Grow mangano-manganic oxide.
Self-supporting three-dimensional grapheme is rinsed well with deionized water, obtains three-dimensional grapheme, then, by three-dimensional grapheme
It is immersed in 4M salpeter solutions 30 minutes, it is 50 DEG C to keep salpeter solution temperature, finally, takes out three-dimensional grapheme and uses deionization
Water cleans up, the three-dimensional grapheme after being cleaned.
The mixed solution of potassium permanganate (0.1mol/L) and sodium nitrate (0.1mol/L) is put into autoclave, after cleaning
Three-dimensional grapheme immerse in the mixed solution of potassium permanganate and sodium nitrate, it is 150 DEG C to keep solution temperature, is grown 30 minutes.
The three-dimensional grapheme being immersed in the mixed solution of potassium permanganate and sodium nitrate is taken out, after being naturally cooling to room temperature,
Drying, obtains three-dimensional grapheme/mangano-manganic oxide combination electrode.
Claims (10)
1. a kind of preparation method based on three-dimensional grapheme/mangano-manganic oxide combination electrode material, comprises the following steps：
(1) substrate pretreatment：
(1a) is ironed by the nickel foam that thickness is 1.6mm using press, obtains the nickel foam thin slice that thickness is 0.25mm；
After (1b) cleans nickel foam thin slice with ethanol, deionized water, 5M HCl solutions, nickel foam thin slice is cleaned with deionized water
Totally, the nickel foam thin slice after being cleaned；
(2) electrochemically depositing copper：
Using electrochemistry three-electrode method, the nickel foam thin slice after cleaning is placed in CuSO4·5H2O and HBO3Mixed solution in,
Chemical deposition voltage is powered up, is deposited 50~150 minutes, obtains covering the nickel foam thin slice of copper；
(3) high annealing：
By cover copper nickel foam thin slice be placed in the flat-temperature zone of chemical vapor deposition CVD tube furnaces, be passed through 5sccm argon gas and
1sccm hydrogen, carries out 1100 DEG C of high annealing 0.5~2 hour, obtains corronil；
(4) electrochemistry selective corrosion：
Using electrochemistry three-electrode method, corronil is placed in CuSO4·5H2O and HBO3Mixed solution in, add corrosion potentials,
Corrode corronil 500~1500 seconds, the three-dimensional corronil skeleton with multichannel hole network structure is prepared；
(5) three-dimensional grapheme/corronil is prepared：
(5a) uses chemical vapour deposition technique, and three-dimensional corronil skeleton is placed in into chemical vapor deposition CVD system tube furnace
In flat-temperature zone, the mixed gas of 20sccm argon gas and hydrogen is passed through 5~10 minutes；
(5b) by diamond heating to 600 DEG C when, be passed through 2~20sccm ethene, keep atmosphere constant, grow 5~10 hours；
(5c) after tubular type furnace temperature is reduced into room temperature, takes out the sample in tube furnace, obtains three-dimensional by the way of cooling rapidly
Graphene/corronil；
(6) self-supporting three-dimensional grapheme is prepared：
Three-dimensional grapheme/corronil is placed in the mixed solution of 0.5~2M iron chloride and 1~3M hydrochloric acid, corroded 24 hours,
Obtain self-supporting three-dimensional grapheme；
(7) mangano-manganic oxide is grown：
(7a) rinses self-supporting three-dimensional grapheme with deionized water well, obtains three-dimensional grapheme；
Three-dimensional grapheme is immersed in 4M salpeter solutions 30 minutes by (7b), is cleaned up after taking-up with deionized water, is obtained clear
Three-dimensional grapheme after washing；
The mixed solution of potassium permanganate and sodium nitrate is put into autoclave by (7c), and the three-dimensional grapheme after cleaning is immersed into Gao Meng
In the mixed solution of sour potassium and sodium nitrate, grow 20~30 minutes；
(7d) takes out the three-dimensional grapheme being immersed in the mixed solution of potassium permanganate and sodium nitrate, after being naturally cooling to room temperature,
Drying, obtains three-dimensional grapheme/mangano-manganic oxide combination electrode.
2. the preparation method according to claim 1 based on three-dimensional grapheme/mangano-manganic oxide combination electrode material, it is special
Sign is, the working electrode in electrochemistry three-electrode method described in step (2) is nickel foam thin slice, reference electrode Ag/
AgCl, auxiliary electrode Pt.
3. the preparation method according to claim 1 based on three-dimensional grapheme/mangano-manganic oxide combination electrode material, it is special
Sign is, the CuSO described in step (2), step (4)4·5H2O and HBO3Mixed solution refer to 0.5~3M CuSO4·
5H2O and 1~2M HBO3Mixed solution.
4. the preparation method according to claim 1 based on three-dimensional grapheme/mangano-manganic oxide combination electrode material, it is special
Sign is that the scope of the electrochemical deposition voltage described in step (2) is -2~-0.2V.
5. the preparation method according to claim 1 based on three-dimensional grapheme/mangano-manganic oxide combination electrode material, it is special
Sign is, the working electrode in electrochemistry three-electrode method described in step (4) is corronil, reference electrode Ag/AgCl,
Auxiliary electrode is Pt.
6. the preparation method according to claim 1 based on three-dimensional grapheme/mangano-manganic oxide combination electrode material, it is special
Sign is that the scope of the corrosion potentials described in step (4) is 0.2~1V.
7. the preparation method according to claim 1 based on three-dimensional grapheme/mangano-manganic oxide combination electrode material, it is special
Sign is that the temperature of the mixed solution of 0.5~2M iron chloride and 1~3M hydrochloric acid described in step (6) is 60~80 DEG C.
8. the preparation method according to claim 1 based on three-dimensional grapheme/mangano-manganic oxide combination electrode material, it is special
Sign is that the temperature of the 4M salpeter solutions described in step (7b) is 50~70 DEG C.
9. the preparation method according to claim 1 based on three-dimensional grapheme/mangano-manganic oxide combination electrode material, it is special
Sign is, potassium permanganate described in step (7c) and in the mixed solution of sodium nitrate, and the concentration of potassium permanganate is 0.1mol/L,
The concentration of sodium nitrate is 0.1mol/L.
10. the preparation method according to claim 1 based on three-dimensional grapheme/mangano-manganic oxide combination electrode material, its
It is characterised by, the temperature of the mixed solution of potassium permanganate and sodium nitrate described in step (7c) is 150~180 DEG C.
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| CN109309217B (en) * | 2018-08-20 | 2021-09-14 | 中国航发北京航空材料研究院 | Preparation method of lithium-sulfur battery positive electrode material |
| CN109461598A (en) * | 2018-09-28 | 2019-03-12 | 新乡学院 | A kind of mangano-manganic oxide self-supporting combination electrode and its preparation method and application |
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