CN109817959A - A kind of C@MnSe nanotube, preparation method and application - Google Patents
A kind of C@MnSe nanotube, preparation method and application Download PDFInfo
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- CN109817959A CN109817959A CN201910249351.9A CN201910249351A CN109817959A CN 109817959 A CN109817959 A CN 109817959A CN 201910249351 A CN201910249351 A CN 201910249351A CN 109817959 A CN109817959 A CN 109817959A
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Abstract
A kind of C@MnSe hollow nanotube provided by the invention, preparation method and application synthesize C@MnSe hollow nanotube composite material using hydro-thermal method twice, and the simple process of synthesis is easy to operate and nontoxic；Uniform hollow nanotube structure is coated and occurred by dopamine completely by the MnSe hollow nanotube that this method synthesizes, and the very thin thickness of nanotube, and sheet surfaces product is larger sufficiently and electrolyte contacts can increase K+Transmission path, improve the performance of battery.Volume expansion of the MnSe hollow nanotube in charge and discharge process can be alleviated after the dopamine carbonization of addition, while carbon material is added, the electric conductivity of material can be improved.
Description
Technical field
The invention belongs to secondary power battery material technical fields, and in particular to a kind of C@MnSe nanotube, preparation method
And application.
Background technique
In recent years, the shortage of resource causes concern of the people to exploitation high performance energy storage equipment, these equipment can
To convert electric energy for other energy or effectively store energy.As a kind of effective energy device, lithium ion battery
(LIBs) portable electronic device is had been widely used for, and is applied to electric car (electric car) and hybrid electric
Automobile (hev), this is because they have the characteristics that high-energy density and long cycle life.But since its reserves is few and price
The direction of research has been extended to the metallic sodium and metallic potassium of same main group by height, scientist.Kalium ion battery oxidation-reduction potential K+/ K (- 2.93V vs.NHE) is close to redox Li+/ Li (- 3.04V and NHE) is lower than Na+/ Na (- 2.71V and NHE),
Make KIBs that there is bigger research potential.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method and application of C@MnSe nanotube, preparation gained size is uniform
C@MnSe hollow nanotube, the C@MnSe hollow nanotube composite material as kalium ion battery negative electrode material have it is excellent
Store up potassium performance.
In order to achieve the above object, The technical solution adopted by the invention is as follows:
A kind of C@MnO provided by the invention2The preparation method of hollow nanotube, comprising the following steps:
S1, potassium permanganate dissolution is obtained into solution A in deionized water, wherein the quality of potassium permanganate and deionized water
Than for (187~250): 30；
S2, it concentrated hydrochloric acid is dissolved in solution A obtains solution B, wherein the matter of the potassium permanganate in concentrated hydrochloric acid and solution A
Amount is than being 7:(2~5)；
S3, solution B is transferred in reaction kettle, natural cooling obtains product C at room temperature after progress drying and processing；
S4, product C is successively obtained into product D after centrifuge separation, washing and drying and processing；
S5, trishydroxymethylaminomethane be dissolved in deionized water obtain solution I, wherein trishydroxymethylaminomethane with
The mass ratio of deionized water is (3~6): 5；
S6, it dopamine is added in solution I obtains solution J, the mass ratio of dopamine and the deionized water in S5 is (2
~4): 5；
S7, it the product D in S4 is added in solution J stirs evenly, obtain mixed solution K, wherein in product D and S5
Deionized water mass ratio be (2~4): 5；
S8, mixed solution K is successively obtained into product M after centrifuge separation, washing and drying and processing；
S9, take product M to be made annealing treatment in an inert atmosphere after to get to C@MnO2Hollow nanotube.
Preferably, 3~6h is made annealing treatment at 30~600 DEG C.
A kind of C@MnO2Hollow nanotube, based on preparation method preparation gained.
A kind of preparation method of C@MnSe hollow nanotube will pass through a kind of C@MnO2The preparation method system of hollow nanotube
Standby resulting C@MnO2Hollow nanotube is uniformly mixed with selenium powder according to the mass ratio of 1:2, and is carried out in an inert atmosphere
Annealing obtains C@MnSe hollow nanotube.
Preferably, 20~60min is made annealing treatment at 800 DEG C.
A kind of C@MnSe hollow nanotube, the preparation method based on a kind of C@MnSe hollow nanotube prepare gained.
A kind of application of C@MnSe hollow nanotube, by a kind of preparation method preparation gained C@of C@MnSe hollow nanotube
Negative electrode material of the MnSe hollow nanotube as kalium ion battery, is assembled into button cell.
Preferably, the specific method for assembling button cell is: cathode uses DMF for solvent, and the formula of pole piece is according to C@
MnSe hollow nanotube: PVDF: acetylene black=9~x:1:x ratio is modulated into slurry, and slurry is then evenly applied to copper foil
On, it is put into vacuum oven and is dried, obtain experimental cell negative electrode tab by punching later, wherein 1≤x≤2；
Using metallic potassium as to electrode；The solution of ethyl carbonate ester and dimethyl carbonate that electrolyte is KPF6 is according to 1:
1 volume ratio is mixed；Diaphragm is celgard2400 film；The sequence of assembled battery is followed successively by negative electrode casing, potassium piece, and diaphragm is born
Pole piece, gasket, spring leaf, anode cover are assembled into button cell in the glove box full of inert atmosphere.
Compared with prior art, beneficial effects of the present invention:
A kind of C@MnO provided by the invention2The preparation method of hollow nanotube, preparing resulting carbon nanotubes can
The biggish nanometer sheet of specific surface area and preferable electric conductivity are provided, and are suitable for K+Pass through, while using between carbon skeleton
Synergistic effect, the conductivity of the active material made, cycle performance and high rate performance are more preferably.
A kind of preparation method of C@MnSe hollow nanotube provided by the invention, it is empty using the synthesis of hydro-thermal method twice C@MnSe
Heart nanometer tube composite materials, the simple process of synthesis are easy to operate and nontoxic.
Manganese selenide is the covalent compound of grey black, belongs to hexagonal crystal system, is had similar to the laminar structured of sandwich,
It is so loose that be combined together by faint Van der Waals force between layers, there are high surface-active and specific surface area, manganese selenide
Compound with carbon, layering N doping porous carbon electrodes make battery have high reversible capacity, good cycle performance.Nano tube structure
Material can also introduce more contact areas between active material and electrolyte, and more live is provided in cyclic process
Property site, increase potassium battery activity, improve potassium battery specific capacity and cycle performance.
It is coated completely by the MnSe hollow nanotube that this method synthesizes by dopamine and uniform hollow nanotube occurs
Structure, the very thin thickness of nanotube, and sheet surfaces product is larger, sufficiently and electrolyte contacts can increase K+Transmission path,
Improve the performance of battery.It is swollen that volume of the MnSe hollow nanotube in charge and discharge process can be alleviated after the dopamine carbonization of addition
It is swollen, while carbon material is added, the electric conductivity of material can be improved.
Detailed description of the invention
Fig. 1 is MnO2The SEM of hollow nanotube schemes；
Fig. 2 is C@MnO2Hollow nanotube SEM figure；
Fig. 3 is C@MnSe hollow nanotube SEM figure；
Specific embodiment
The present invention provides a kind of preparation methods of C@MnSe hollow nanotube, using MnO2Nanotube is as forerunner
Body, by selenizing, packet carbon forms C@MnSe hollow nanotube.The biggish nanometer of specific surface area is provided using carbon nanotubes
Piece and preferable electric conductivity, and be suitable for K+Pass through, while using the synergistic effect between carbon skeleton, the active material made
The conductivity of material, cycle performance and high rate performance are more preferably.
It please refers to shown in figure, a kind of preparation method of C@MnSe hollow nanotube of the present invention, comprising the following steps:
Potassium permanganate dissolution is obtained solution A by S1, under magnetic stirring in deionized water, wherein potassium permanganate with go
The mass ratio of ionized water is (187~250): 30；
The concentrated hydrochloric acid that mass concentration is 37% is dissolved in solution A and obtains solution B by S2, under magnetic stirring, wherein
The mass ratio for the potassium permanganate in concentrated hydrochloric acid and solution A that mass concentration is 37% is 7:(2~5)；
S3, B solution is transferred in reaction kettle, be placed in baking oven 120~200 DEG C react 12~for 24 hours, then in room temperature
Lower natural cooling obtains product C；
S4, product C being centrifugated by 10000~15000rpm, deionized water and ethanol washing are washed repeatedly, 60~
80 DEG C of drying 6~obtain product D afterwards for 24 hours；
S5, in the case of stirring, weighs trishydroxymethylaminomethane and is dissolved in deionized water and obtain solution I, wherein three
Hydroxymethyl aminomethane and the mass ratio of deionized water are (3~6): 5；
S6, in the case of stirring, dopamine is added in solution I and obtains solution J, the deionization in dopamine and S5
The mass ratio of water is (2~4): 5；
Product D is added to stirring 12 in solution J~for 24 hours, obtains mixed solution K by S7, in the case of stirring, wherein
The mass ratio of deionized water in product D and S5 is (2~4): 5；
S8, mixed solution K being centrifugated by 10000~15000rpm, deionized water and ethanol washing are washed repeatedly,
60~80 DEG C of drying 6~obtain product M afterwards for 24 hours；
S9, taking product M, annealing obtains C@MnO at 30~600 DEG C, 3~6h in an inert atmosphere2Hollow nanotube
N；
S10, take product N and selenium powder according to 1:2 ratio be uniformly mixed and in an inert atmosphere at 800 DEG C, 20~
60min makes annealing treatment to obtain C@MnSe hollow nanotube.
In S9, annealing temperature is 550 DEG C, annealing time 3h.
The application of kalium ion battery prepared by the present invention C@MnSe hollow nanotube negative electrode material, C@MnSe hollow Nano
Pipe composite material is applied to button cell, and cathode uses DMF as the solvent for dissolving PVDF, and the formula of pole piece is hollow according to C@MnSe
Nanotube: PVDF: the ratio of acetylene black=9-x:1:x (1≤x≤2) is modulated into slurry, and slurry is then coated uniformly on copper foil
On, it is put into after after 60 DEG C of bakings for 24 hours, being washed into the disk that diameter is 12mm in vacuum oven and obtains experimental cell pole piece, with gold
Belong to potassium to be used as to electrode, ethyl carbonate ester that electrolyte is 1.0M KPF6 (EC and dimethyl carbonate (volume ratio 1:1) it is molten
Liquid, diaphragm are celgard2400 film, are assembled into button cell in the glove box full of argon atmosphere.
Button cell charge and discharge blanking voltage is 0.01-2.6V, and charging or discharging current density is 50mA/g-1000mA/g.
Embodiment 1
(1) under magnetic stirring, 500g potassium permanganate is dissolved in 30mL deionized water and obtains solution A；
(2) under magnetic stirring, the concentrated hydrochloric acid that 0.6mL mass concentration is 37% is dissolved in solution A and obtains solution B；
(3) B solution is transferred in clean reaction kettle, is placed in 200 DEG C of baking ovens and reacts 12h, then at room temperature certainly
So cooling obtains product C；
(4) solvent-thermal process product C being centrifugated by 10000rpm, deionized water and ethanol washing are washed repeatedly,
Product D is obtained after 80 DEG C of drying 6h；
In the case of stirring, (5), weigh 0.18g trishydroxymethylaminomethane be dissolved in deionized water 150mL obtain it is molten
Liquid I；
(6), in the case of stirring, 0.06g dopamine is added in solution I and obtains solution J；
In the case of stirring, (7), it is added in solution J in product D and obtains solution K after 12h；
(8), synthetic product K is centrifugated by 10000rpm, and deionized water and ethanol washing are washed repeatedly, 60 DEG C of drying
Obtain product M afterwards for 24 hours
(9), taking product M, annealing obtains C@MnO at 300 DEG C of 3h in argon atmosphere2Hollow nanotube N.
(10), C@MnO is taken2Hollow nanotube N 0.1g and 0.2g selenium powder is annealed at 800 DEG C of 20min in argon atmosphere
Processing obtains C@MnSe hollow nanotube.
Embodiment 2
(1) under magnetic stirring, 400g potassium permanganate is dissolved in 30mL deionized water and obtains solution A；
(2) under magnetic stirring, the concentrated hydrochloric acid that 0.5mL mass concentration is 37% is dissolved in solution A and obtains solution B；
(3) B solution is transferred in clean reaction kettle, is placed in 120 DEG C of baking ovens and reacts 12h, then at room temperature certainly
So cooling obtains product C；
(4) solvent-thermal process product C being centrifugated by 10000rpm, deionized water and ethanol washing are washed repeatedly,
Product D is obtained after 80 DEG C of drying 6h；
In the case of stirring, (5), weigh 0.18g trishydroxymethylaminomethane be dissolved in deionized water 150mL obtain it is molten
Liquid I；
(6), in the case of stirring, 0.12g dopamine is added in solution I and obtains solution J；
In the case of stirring, (7), it is added in solution J in product D and obtains solution K after 12h；
(8), synthetic product K is centrifugated by 10000rpm, and deionized water and ethanol washing are washed repeatedly, 60 DEG C of drying
Obtain product M afterwards for 24 hours
(9), taking product M, annealing obtains C@MnO at 300 DEG C of 3h in argon atmosphere2Hollow nanotube N.
(10), taking product N 0.1g and 0.2g selenium powder, annealing obtains C@at 800 DEG C of 20min in argon atmosphere
MnSe hollow nanotube.
Embodiment 3
(1) under magnetic stirring, 500g potassium permanganate is dissolved in 30mL deionized water and obtains solution A；
(2) under magnetic stirring, the concentrated hydrochloric acid that 0.6mL mass concentration is 37% is dissolved in solution A and obtains solution B；
(3) B solution is transferred in clean reaction kettle, is placed in 180 DEG C of baking ovens and reacts 12h, then at room temperature certainly
So cooling obtains product C；
(4) solvent-thermal process product C being centrifugated by 10000rpm, deionized water and ethanol washing are washed repeatedly,
Product D is obtained after 80 DEG C of drying 6h；
In the case of stirring, (5), weigh 0.09g trishydroxymethylaminomethane be dissolved in deionized water 150mL obtain it is molten
Liquid I；
(6), in the case of stirring, 0.06g dopamine is added in solution I and obtains solution J；
In the case of stirring, (7), it is added in solution J in product D and obtains solution K after 12h；
(8), synthetic product K is centrifugated by 10000rpm, and deionized water and ethanol washing are washed repeatedly, 60 DEG C of drying
Obtain product M afterwards for 24 hours
(9), taking product M, annealing obtains C@MnO at 500 DEG C of 3h in argon atmosphere2Hollow nanotube N.
(10), taking product N 0.1g and 0.2g selenium powder, annealing obtains C@at 800 DEG C of 20min in argon atmosphere
MnSe hollow nanotube.
Embodiment 4
(1) under magnetic stirring, 300g potassium permanganate is dissolved in 30mL deionized water and obtains solution A；
(2) under magnetic stirring, the concentrated hydrochloric acid that 0.6mL mass concentration is 37% is dissolved in solution A and obtains solution B；
(3) B solution is transferred in clean reaction kettle, is placed in 120 DEG C of baking ovens and reacts 12h, then at room temperature certainly
So cooling obtains product C；
(4) solvent-thermal process product C being centrifugated by 10000rpm, deionized water and ethanol washing are washed repeatedly,
Product D is obtained after 80 DEG C of drying 6h；
In the case of stirring, (5), weigh 0.18g trishydroxymethylaminomethane be dissolved in deionized water 150mL obtain it is molten
Liquid I；
(6), in the case of stirring, 0.12g dopamine is added in solution I and obtains solution J；
In the case of stirring, (7), it is added in solution J in product D and obtains solution K after 12h；
(8), synthetic product K is centrifugated by 10000rpm, and deionized water and ethanol washing are washed repeatedly, 60 DEG C of drying
Obtain product M afterwards for 24 hours
(9), taking product M, annealing obtains C@MnO at 300 DEG C of 3h in argon atmosphere2Hollow nanotube N.
(10), taking product N 0.2g and 0.4g selenium powder, annealing obtains C@at 800 DEG C of 30min in argon atmosphere
MnSe hollow nanotube.
Embodiment 5
(1) under magnetic stirring, 0.264g potassium permanganate is dissolved in 30mL deionized water and obtains solution A；
(2) under magnetic stirring, the concentrated hydrochloric acid that 0.6mL mass concentration is 37% is dissolved in solution A and obtains solution B；
(3) B solution is transferred in clean reaction kettle, is placed in 180 DEG C of baking ovens and reacts 12h, then at room temperature certainly
So cooling obtains product C；
(4) solvent-thermal process product C being centrifugated by 10000rpm, deionized water and ethanol washing are washed repeatedly,
Product D is obtained after 80 DEG C of drying 6h；
In the case of stirring, (5), weigh 0.18g trishydroxymethylaminomethane be dissolved in deionized water 150mL obtain it is molten
Liquid I；
(6), in the case of stirring, 0.06g dopamine is added in solution I and obtains solution J；
In the case of stirring, (7), it is added in solution J in product D and obtains solution K after 12h；
(8), synthetic product K is centrifugated by 10000rpm, and deionized water and ethanol washing are washed repeatedly, 60 DEG C of drying
Obtain product M afterwards for 24 hours
(9), taking product M, annealing obtains C@MnO at 300 DEG C of 3h in argon atmosphere2Hollow nanotube N.
(10), taking product N 0.1g and 0.2g selenium powder, annealing obtains C@at 800 DEG C of 20min in argon atmosphere
MnSe hollow nanotube.
Embodiment 6
(1) under magnetic stirring, 500g potassium permanganate is dissolved in 30mL deionized water and obtains solution A；
(2) under magnetic stirring, the concentrated hydrochloric acid that 0.6mL mass concentration is 37% is dissolved in solution A and obtains solution B；
(3) B solution is transferred in clean reaction kettle, is placed in 120 DEG C of baking ovens and reacts for 24 hours, then at room temperature certainly
So cooling obtains product C；
(4) solvent-thermal process product C being centrifugated by 10000rpm, deionized water and ethanol washing are washed repeatedly,
Product D is obtained after 80 DEG C of drying 6h；
In the case of stirring, (5), weigh 0.18g trishydroxymethylaminomethane be dissolved in deionized water 150mL obtain it is molten
Liquid I；
(6), in the case of stirring, 0.06g dopamine is added in solution I and obtains solution J；
In the case of stirring, (7), it is added in solution J in product D and obtains solution K after 12h；
(8), synthetic product K is centrifugated by 10000rpm, and deionized water and ethanol washing are washed repeatedly, 60 DEG C of drying
Obtain product M afterwards for 24 hours
(9), taking product M, annealing obtains C@MnO at 300 DEG C of 3h in argon atmosphere2Hollow nanotube N.
(10), taking product N 0.6g and 1.2g selenium powder, annealing obtains C@at 800 DEG C of 40min in argon atmosphere
MnSe hollow nanotube.
Embodiment 7
(1) under magnetic stirring, 264g potassium permanganate is dissolved in 30mL deionized water and obtains solution A；
(2) under magnetic stirring, the concentrated hydrochloric acid that 0.6mL mass concentration is 37% is dissolved in solution A and obtains solution B；
(3) B solution is transferred in clean reaction kettle, is placed in 120 DEG C of baking ovens and reacts 12h, then at room temperature certainly
So cooling obtains product C；
(4) solvent-thermal process product C being centrifugated by 10000rpm, deionized water and ethanol washing are washed repeatedly,
Product D is obtained after 80 DEG C of drying 6h；
In the case of stirring, (5), weigh 0.18g trishydroxymethylaminomethane be dissolved in deionized water 150mL obtain it is molten
Liquid I；
(6), in the case of stirring, 0.06g dopamine is added in solution I and obtains solution J；
In the case of stirring, (7), it is added in solution J in product D and obtains solution K after 12h；
(8), synthetic product K is centrifugated by 10000rpm, and deionized water and ethanol washing are washed repeatedly, 60 DEG C of drying
Obtain product M afterwards for 24 hours
(9), taking product M, annealing obtains C@MnO at 300 DEG C of 3h in argon atmosphere2Hollow nanotube N.
(10), taking product N 0.1g and 0.2g selenium powder, annealing obtains C@at 800 DEG C of 60min in argon atmosphere
MnSe hollow nanotube.
Fig. 1 is MnO2The SEM of hollow nanotube schemes.As can be seen from the figure the even thickness of nanotube, nanotube it is straight
Diameter in 50-100nm, be convenient for its appearance into the modification of property carbon by small size；
Fig. 2 is C@MnO2Hollow nanotube SEM figure.As can be seen from the figure MnO2The surface of nanotube has coated one layer of carbon,
The thickness of nanotube is increased, and diameter uniform in size is about between 100-250nm；
Fig. 3 is C@MnSe hollow nanotube SEM figure.The C@MnSe hollow nanotube prepared by high temperature solid-state method, can be from
It can be seen that the size of nanotube is 200-300nm in figure, size is uniform.
Claims (8)
1. a kind of C@MnO2The preparation method of hollow nanotube, which comprises the following steps:
S1, potassium permanganate dissolution is obtained into solution A in deionized water, wherein potassium permanganate and the mass ratio of deionized water are
(187~250): 30；
S2, it concentrated hydrochloric acid is dissolved in solution A obtains solution B, wherein the mass ratio of the potassium permanganate in concentrated hydrochloric acid and solution A
For 7:(2~5)；
S3, solution B is transferred in reaction kettle, natural cooling obtains product C at room temperature after progress drying and processing；
S4, product C is successively obtained into product D after centrifuge separation, washing and drying and processing；
S5, trishydroxymethylaminomethane be dissolved in deionized water obtain solution I, wherein trishydroxymethylaminomethane and go from
The mass ratio of sub- water is (3~6): 5；
S6, it dopamine is added in solution I obtains solution J, the mass ratio of dopamine and the deionized water in S5 is (2~4):
5；
S7, it the product D in S4 is added in solution J stirs evenly, obtain mixed solution K, wherein go in product D and S5
The mass ratio of ionized water is (2~4): 5；
S8, mixed solution K is successively obtained into product M after centrifuge separation, washing and drying and processing；
S9, take product M to be made annealing treatment in an inert atmosphere after to get to C@MnO2Hollow nanotube.
2. a kind of C@MnO according to claim 12The preparation method of hollow nanotube, which is characterized in that in S9, at annealing
The process conditions of reason: 3~6h is made annealing treatment at 30~600 DEG C.
3. a kind of C@MnO2Hollow nanotube, which is characterized in that based on preparation method described in claim 1 preparation gained.
4. a kind of preparation method of C@MnSe hollow nanotube, which is characterized in that a kind of C@described in claim 1 will be passed through
MnO2The preparation method of hollow nanotube prepares resulting C@MnO2Hollow nanotube and selenium powder are mixed according to the mass ratio of 1:2
It closes uniformly, and is made annealing treatment to obtain C@MnSe hollow nanotube in an inert atmosphere.
5. a kind of preparation method of C@MnSe hollow nanotube according to claim 4, which is characterized in that the technique of annealing
Condition is: 20~60min is made annealing treatment at 800 DEG C.
6. a kind of C@MnSe hollow nanotube, which is characterized in that receive based on a kind of C@MnSe described in claim 4 or 5 is hollow
The preparation method of mitron prepares gained.
7. a kind of application of C@MnSe hollow nanotube, which is characterized in that a kind of C@MnSe described in claim 4 or 5 is empty
Negative electrode material of the preparation method preparation gained C@MnSe hollow nanotube of heart nanotube as kalium ion battery, is assembled into button
Battery.
8. a kind of application of C@MnSe hollow nanotube according to claim 7, which is characterized in that assemble button cell
Specific method is: cathode uses DMF for solvent, and the formula of pole piece is according to C@MnSe hollow nanotube: PVDF: acetylene black=9~
The mass ratio of x:1:x is modulated into slurry, and then slurry is evenly applied on copper foil, is put into vacuum oven and is dried,
Experimental cell negative electrode tab is obtained by punching later, wherein 1≤x≤2；
Using metallic potassium as to electrode；The solution of ethyl carbonate ester and dimethyl carbonate that electrolyte is KPF6 is according to 1:1's
Volume ratio is mixed；Diaphragm is celgard2400 film；The sequence of assembled battery is followed successively by negative electrode casing, potassium piece, diaphragm, cathode
Piece, gasket, spring leaf, anode cover are assembled into button cell in the glove box full of inert atmosphere.
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| CN112186182A (en) * | 2020-09-10 | 2021-01-05 | 青岛科技大学 | One-dimensional hollow carbon-coated iron selenide nanotube composite electrode material and preparation method thereof |
| CN114420908A (en) * | 2022-01-11 | 2022-04-29 | 西北工业大学 | Graphene-loaded nitrogen-doped carbon-coated manganese selenide-based sodium/potassium ion battery cathode material and preparation method thereof |
| CN115117457A (en) * | 2022-08-26 | 2022-09-27 | 河南师范大学 | Preparation method of potassium ion full-cell device |
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| CN110416542A (en) * | 2019-07-30 | 2019-11-05 | 山东大学 | Porous manganese selenide microballoon, preparation method, positive electrode and battery |
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| CN114420908A (en) * | 2022-01-11 | 2022-04-29 | 西北工业大学 | Graphene-loaded nitrogen-doped carbon-coated manganese selenide-based sodium/potassium ion battery cathode material and preparation method thereof |
| CN115117457A (en) * | 2022-08-26 | 2022-09-27 | 河南师范大学 | Preparation method of potassium ion full-cell device |
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