CN109817961A - A kind of cladding Co0.85Se Prussian blue analogue nano square, preparation method and application - Google Patents
A kind of cladding Co0.85Se Prussian blue analogue nano square, preparation method and application Download PDFInfo
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Abstract
A kind of cladding Co provided by the invention0.85Se Prussian blue analogue nano square, preparation method and application, the Co coated using hydro-thermal method synthesizing graphite alkene twice0.85Se Prussian blue analogue composite material, the simple process of synthesis are easy to operate and nontoxic.The Co of synthesis0.85Se Prussian blue analogue is coated completely and occurred by graphene uniform nano flower square, nano square it is uniform in size, and surface area is larger, sufficiently and electrolyte contacts can increase K+Transmission path, improve the performance of battery.The electric conductivity of active material can be enhanced in the graphene of addition electric conductivity with higher, and graphene has biggish specific surface area, can increase the contact area with electrolyte.
Description
Technical field
The invention belongs to secondary power battery material technical fields, and in particular to a kind of cladding Co0.85Se Prussian blue analogue
Nano square, preparation method and application.
Background technique
Graphene is that a kind of carbon atom covalent bond with sp2 hydridization combines the monatomic two dimension formed with hexagon phenyl ring
Planar structure.Graphene is ultralight with specific gravity, specific surface area is very big, excellent thermal conductivity and mechanical performance, carrier's rate are high
Up to 2 × 105cm2.The electric conductivity of graphene is extremely strong, and electron mobility is up to 15000cm under room temperature2/ (VS), resistivity only has
About 8~10 Ω are the smallest materials of resistivity, and from a manufacturing perspective, there is abundant and cheap production graphene in China
Raw graphite makes China have certain advantage in graphene research.But electrode material of the graphene as kalium ion battery
Material, the piece interlamellar spacing of graphene is wider, in K+Easily reunite during insertion and abjection.
Summary of the invention
The purpose of the present invention is to provide a kind of kalium ion battery negative electrode material graphene coated Co0.85Se Prussian blue analogue
Nano square, preparation method and application, its object is to obtain uniform graphene coated Co0.85Se Prussian blue analogue is received
Rice square, by graphene coated Co0.85Se Prussian blue analogue nano square has excellent as kalium ion battery negative electrode material
Store up potassium performance.
In order to achieve the above object, The technical solution adopted by the invention is as follows:
A kind of kalium ion battery negative electrode material graphene coated Co provided by the invention0.85Se Prussian blue analogue nano square
Preparation method, comprising the following steps:
S1, cobalt acetate and sodium citrate mixed dissolution are obtained into solution A in deionized water, wherein cobalt acetate and citric acid
The mass ratio of sodium is 1:(1~2), the mass ratio of cobalt acetate and deionized water is (0.3~0.6): 20；
S2, Cobalt Potassium Cyanide dissolution is obtained into solution B in deionized water, wherein the matter of Cobalt Potassium Cyanide and cobalt acetate
Amount is than being (1~2): 1；
S3, by solution A be poured into solution B be uniformly mixed, at room temperature stir certain time obtain product C；
S4, product C is successively passed through to centrifuge separation, washing and drying and processing, obtains product D；
S5, it takes product D to be dissolved into the mixed liquor being made of the dispersion liquid of deionized water and graphene and carries out ultrasonic place
Reason obtains solution E；
S6, it is sufficiently mixed in solution E addition sodium selenite, obtains solution F, wherein the quality of sodium selenite and cobalt acetate
Than for (2~3): 1；
S7, in solution F be added hydrazine hydrate obtain Solution H, wherein the mass ratio of hydrazine hydrate and cobalt acetate be (0.5~
1):2；
S8, Solution H is transferred in reaction kettle, is placed in baking oven and is dried, then natural cooling obtains at room temperature again
Product I；
S9, synthetic product I is centrifuged, is washed and drying and processing, obtaining the Co of graphene coated0.85The general Shandong of Se class
The square of scholar's indigo plant.
Preferably, in S4, the technological parameter of centrifuge separation are as follows: (10000~15000) rpm.
Preferably, in S5, the mass ratio of deionized water and graphene dispersing solution is (0.003~0.001): 17；Product D with
The mass ratio of deionized water is 0.025:17.
Preferably, in S8, the process conditions of reaction kettle: temperature be 160~200 DEG C, the reaction time be 12~for 24 hours.
Preferably, in S9, the process conditions of product I centrifuge separation and drying and processing: 10000~15000rpm of eccentricity,
60~80 DEG C of drying 12~for 24 hours.
A kind of kalium ion battery negative electrode material graphene coated class Co0.85Se Prussian blue analogue nano square, based on described
Preparation method prepare gained.
A kind of application coating class Co0.85Se Prussian blue analogue nano square, by graphene coated class Co0.85Se class is general
Negative electrode material of the Shandong scholar's indigo plant nano square 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 graphite
Alkene coats class Co0.85Se Prussian blue analogue nano square: PVDF: acetylene black=9~x:1:x mass ratio is modulated into slurry, so
Slurry is evenly applied on copper foil afterwards, is put into vacuum oven and is dried, obtains experimental cell use by punching later
Negative electrode tab, 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, the invention has the benefit that
A kind of cladding Co provided by the invention0.85The preparation method of Se Prussian blue analogue nano square, using hydro-thermal twice
The Co of method synthesizing graphite alkene cladding0.85Se Prussian blue analogue composite material, the simple process of synthesis are easy to operate and nontoxic.Synthesis
Co0.85Se Prussian blue analogue is coated completely and occurred by graphene uniform nano flower square, nano square it is uniform in size,
And surface area is larger；Its unique structure C o of transistion metal compound0.85Se Prussian blue analogue nano square has hollow structure,
It can reduce the resistance of potassium ion insertion and abjection.The Co with hollow structure of graphene coated0.85Se lamellar compound is made
Shown for kalium ion battery negative electrode material excellent battery specific capacity and stable cycle performance, wherein graphene provide compared with
Big specific surface area and excellent electric conductivity.
Detailed description of the invention
Fig. 1 is that the SEM of Co-Co Prussian blue analogue nano square schemes；
Fig. 2 is that the SEM of graphene coated Co0.85Se Prussian blue analogue nano square schemes；
Fig. 3 is the XRD diagram of graphene coated Co0.85Se Prussian blue analogue nano square；
Fig. 4 is the charge-discharge performance figure of graphene coated Co0.85Se Prussian blue analogue nano square.
Specific embodiment
The present invention provides a kind of cladding Co0.85The preparation method of Se Prussian blue analogue nano square, using graphene packet
Cover Co0.85Se Prussian blue analogue nano square.More stable skeleton is provided using graphene, preferable electric conductivity and biggish
Specific surface area, and the larger suitable K of interlamellar spacing of graphene+Pass through, the conductivity of the active material made, cycle performance and
High rate performance is more preferably.
It please refers to shown in figure, a kind of preparation method for coating Co0.85Se Prussian blue analogue nano square of the present invention, including
Following steps:
S1, under stiring, obtains solution A for cobalt acetate and sodium citrate mixed dissolution, wherein acetic acid in deionized water
The mass ratio of cobalt and sodium citrate is 1:(1~2), the mass ratio of cobalt acetate and deionized water is (0.3~0.6): 20；
Cobalt Potassium Cyanide dissolution is obtained solution B, Cobalt Potassium Cyanide and cobalt acetate by S2, under stiring in deionized water
Mass ratio be (1~2): 1；
Solution A is poured into solution B and is uniformly mixed by S3, under stiring, stirs 12~20h at room temperature and obtains product C；
S4, product C is centrifugated through 10000~15000rpm, 60~80 DEG C of drying 12~obtain product D afterwards for 24 hours
S5, it takes that product D is dissolved into the mixed solution of deionized water and graphene dispersing solution and ultrasound obtains solution E, produces
Object D and the mass ratio of deionized water are 0.025:17, the mass ratio of deionized water and graphene dispersing solution be (0.003~
0.001): 17；Ultrasonic time is 30~60min；
After the completion of S6, ultrasound under magnetic stirring, sodium selenite is added in solution E and obtains solution F, sodium selenite and acetic acid
The mass ratio of cobalt is (2~3): 1；
Hydrazine hydrate is added in solution F and obtains Solution H by S7, under magnetic stirring, and the mass ratio of hydrazine hydrate and cobalt acetate is
(0.5-1):2；
S8, Solution H is transferred in clean reaction kettle, is placed in baking oven and is reacting, then natural cooling at room temperature again
Obtaining product I, the reaction temperature of reaction kettle in an oven is 160~200 DEG C, the reaction time is 12~for 24 hours；
S9, product I are centrifugated through 10000~15000rpm, 60~80 DEG C of drying 12~obtain product J afterwards for 24 hours as stone
The Co of black alkene cladding0.85Se Prussian blue analogue nano square.
Kalium ion battery prepared by the present invention graphene coated Co0.85Se Prussian blue analogue nano square negative electrode material
Using graphene coated Co0.85Se Prussian blue analogue nano square composite material be applied to button cell, cathode use DMF for
The solvent of PVDF is dissolved, the formula of pole piece is according to graphene coated Co0.85Se Prussian blue analogue nano square: PVDF: acetylene black
The mass ratio of=9~x:1:x (1≤x≤2) is modulated into slurry, and then slurry is coated uniformly on copper foil, is put into vacuum drying
In case after 80 DEG C of baking 12h, experimental cell pole piece is obtained after being washed into the disk that diameter is 12mm, using metallic potassium as to electrode,
Electrolyte is that the ethyl carbonate ester that electrolyte is KPF6 is mixed with the solution of dimethyl carbonate according to the volume ratio of 1:1,
Diaphragm is Whatman film, is 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.
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.The present invention being described and shown in usually here in attached drawing is real
The component for applying example can be arranged and be designed by a variety of different configurations.Therefore, below to the present invention provided in the accompanying drawings
The detailed description of embodiment be not intended to limit the range of claimed invention, but be merely representative of of the invention selected
Embodiment.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
The every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
(1), under stiring, 400mg cobalt acetate and 260mg sodium citrate mixed dissolution are obtained in removing 20mL ionized water
Solution A；
(2), under stiring, 0.28g Cobalt Potassium Cyanide is dissolved in 20m deionized water and obtains solution B,；
(3), under stiring, solution A is poured into B solution and is uniformly mixed, 12h is stirred at room temperature and obtains product C；
(4), synthetic product C is centrifugated through 10000rpm, obtains product D after 60 DEG C of drying 12h
(5), it takes that 120mg D is dissolved into 17mL ionized water and 3mL graphene dispersing solution and ultrasound obtains solution E, surpasses
The sound time is 30min；
(6), 60mg sodium selenite after the completion of ultrasound under magnetic stirring, is added in solution E and obtains solution F；
(7), 5mL hydrazine hydrate under magnetic stirring, is added in solution F and obtains Solution H；
(8), H solution is transferred in clean reaction kettle, is placed in baking oven and is reacting, then natural cooling at room temperature again
Product I is obtained, the reaction temperature of reaction kettle in an oven is 160 DEG C, reaction time 12h；
(9), product I is centrifugated through 10000rpm, obtains product J after 60 DEG C of drying 12h.
Embodiment 2
(1), under stiring, 300mg cobalt acetate and 260mg sodium citrate mixed dissolution are obtained in removing 20mL ionized water
Solution A；
(2), under stiring, 0.28g Cobalt Potassium Cyanide is dissolved in 20m deionized water and obtains solution B,；
(3), under stiring, solution A is poured into B solution and is uniformly mixed, 12h is stirred at room temperature and obtains product C；
(4), synthetic product C is centrifugated through 12000rpm, obtains product D after 70 DEG C of drying 16h
(5), it takes that 120mg D is dissolved into 15mL ionized water and 5mL graphene dispersing solution and ultrasound obtains solution E, surpasses
The sound time is 30min；
(6), 45mg sodium selenite after the completion of ultrasound under magnetic stirring, is added in solution E and obtains solution F；
(7), 5mL hydrazine hydrate under magnetic stirring, is added in solution F and obtains Solution H；
(8), H solution is transferred in clean reaction kettle, is placed in baking oven and is reacting, then natural cooling at room temperature again
Product I is obtained, the reaction temperature of reaction kettle in an oven is 180 DEG C, reaction time 16h；
(9), product I is centrifugated through 10000rpm, obtains product J after 80 DEG C of drying 12h；
Embodiment 3
(1), under stiring, 200mg cobalt acetate and 260mg sodium citrate mixed dissolution are obtained in removing 20mL ionized water
Solution A；
(2), under stiring, 0.28g Cobalt Potassium Cyanide is dissolved in 20m deionized water and obtains solution B,；
(3), under stiring, solution A is poured into B solution and is uniformly mixed, 12h is stirred at room temperature and obtains product C；
(4), synthetic product C is centrifugated through 10000rpm, obtains product D after 60 DEG C of drying 12h
(5), it takes that 120mg D is dissolved into 18mL ionized water and 2mL graphene dispersing solution and ultrasound obtains solution E, surpasses
The sound time is 30min；
(6), 60mg sodium selenite after the completion of ultrasound under magnetic stirring, is added in solution E and obtains solution F；
(7), 5mL hydrazine hydrate under magnetic stirring, is added in solution F and obtains Solution H；
(8), H solution is transferred in clean reaction kettle, is placed in baking oven and is reacting, then natural cooling at room temperature again
Product I is obtained, the reaction temperature of reaction kettle in an oven is 160 DEG C, reaction time 20h；
(9), product I is centrifugated through 10000rpm, obtains product J after 60 DEG C of drying 12h；
Embodiment 4
(1), under stiring, 200mg cobalt acetate and 260mg sodium citrate mixed dissolution are obtained in removing 20mL ionized water
Solution A；
(2), under stiring, 0.28g Cobalt Potassium Cyanide is dissolved in 20mL deionized water and obtains solution B,；
(3), under stiring, solution A is poured into B solution and is uniformly mixed, 12h is stirred at room temperature and obtains product C；
(4), synthetic product C is centrifugated through 10000rpm, obtains product D after 60 DEG C of drying 12h
(5), it takes that 120mg D is dissolved into 19mL ionized water and 1mL graphene dispersing solution and ultrasound obtains solution E, surpasses
The sound time is 30min；
(6), 60mg sodium selenite after the completion of ultrasound under magnetic stirring, is added in solution E and obtains solution F；
(7), 5mL hydrazine hydrate under magnetic stirring, is added in solution F and obtains Solution H；
(8), H solution is transferred in clean reaction kettle, is placed in baking oven and is reacting, then natural cooling at room temperature again
Product I is obtained, the reaction temperature of reaction kettle in an oven is 160 DEG C, reaction time 18h；
(9), product I is centrifugated through 10000rpm, obtains product J after 60 DEG C of drying 12h；
Embodiment 5
(1), under stiring, 200mg cobalt acetate and 260mg sodium citrate mixed dissolution are obtained in removing 20mL ionized water
Solution A；
(2), under stiring, 0.28g Cobalt Potassium Cyanide is dissolved in 20m deionized water and obtains solution B,；
(3), under stiring, solution A is poured into B solution and is uniformly mixed, 12h is stirred at room temperature and obtains product C；
(4), synthetic product C is centrifugated through 10000rpm, obtains product D after 60 DEG C of drying 12h
(5), it takes that 120mg D is dissolved into 17mL ionized water and 3mL graphene dispersing solution and ultrasound obtains solution E, surpasses
The sound time is 30min；
(6), 30mg sodium selenite after the completion of ultrasound under magnetic stirring, is added in solution E and obtains solution F；
(7), 1mL hydrazine hydrate under magnetic stirring, is added in solution F and obtains Solution H；
(8), H solution is transferred in clean reaction kettle, is placed in baking oven and is reacting, then natural cooling at room temperature again
Product I is obtained, the reaction temperature of reaction kettle in an oven is 160 DEG C, reaction time 16h；
(9), product I is centrifugated through 10000rpm, obtains product J after 60 DEG C of drying 12h；
Embodiment 6
(1), under stiring, 200mg cobalt acetate and 260mg sodium citrate mixed dissolution are obtained in 20mL deionized water
Solution A；
(2), under stiring, 0.28g Cobalt Potassium Cyanide is dissolved in 20m deionized water and obtains solution B,；
(3), under stiring, solution A is poured into B solution and is uniformly mixed, 12h is stirred at room temperature and obtains product C；
(4), synthetic product C is centrifugated through 10000rpm, obtains product D after 60 DEG C of drying 12h
(5), it takes that 120mg D is dissolved into 17mL ionized water and 3mL graphene dispersing solution and ultrasound obtains solution E, surpasses
The sound time is 30min；
(6), 60mg sodium selenite after the completion of ultrasound under magnetic stirring, is added in solution E and obtains solution F；
(7), 2mL hydrazine hydrate under magnetic stirring, is added in solution F and obtains Solution H；
(8), H solution is transferred in clean reaction kettle, is placed in baking oven and is reacting, then natural cooling at room temperature again
Product I is obtained, the reaction temperature of reaction kettle in an oven is 160 DEG C, reaction time 10h；
(9), product I is centrifugated through 10000rpm, obtains product J after 60 DEG C of drying 12h；
Embodiment 7
(1), under stiring, 200mg cobalt acetate and 260mg sodium citrate mixed dissolution are obtained in removing 20mL ionized water
Solution A；
(2), under stiring, 0.28g Cobalt Potassium Cyanide is dissolved in 20m deionized water and obtains solution B,；
(3), under stiring, solution A is poured into B solution and is uniformly mixed, 12h is stirred at room temperature and obtains product C；
(4), synthetic product C is centrifugated through 10000rpm, obtains product D after 60 DEG C of drying 12h
(5), it takes that 120mg D is dissolved into 17mL ionized water and 3mL graphene dispersing solution and ultrasound obtains solution E, surpasses
The sound time is 30min；
(6), 60mg sodium selenite after the completion of ultrasound under magnetic stirring, is added in solution E and obtains solution F；
(7), 3mL hydrazine hydrate under magnetic stirring, is added in solution F and obtains Solution H；
(8), H solution is transferred in clean reaction kettle, is placed in baking oven and is reacting, then natural cooling at room temperature again
Product I is obtained, the reaction temperature of reaction kettle in an oven is 200 DEG C, and the reaction time is for 24 hours；
(9), product I is centrifugated through 10000rpm, obtains product J after 60 DEG C of drying 12h；
By the implementation tested above, the graphene coated Co that embodiment 4 obtains is found0.85Se Prussian blue analogue nanometer side
Block, pattern more evenly, are conducive to K+Insertion and abjection.
Nano square proper alignment as can see from Figure 1, and it is uniform in size, surface is smooth, does not adhere to other
Grain.The side length of nano square is about 500nm.
The lamellar structure of graphene is coated with Co as seen from Figure 20.85The nano particle of Se.Graphene is with higher
The nano square of specific surface area and higher electric conductivity, the compound of the Prussian blue analogue of Co-Co is suitble to alkali metal ion
Insertion and abjection, can suitably alleviate the volume expansion of electrode material.
From figure 3, it can be seen that 2 θ be 33.2 °, 44.7 °, 50.5 °, 60.3 ° and, 61.8 ° of corresponding Co0.85Se PDF card
Piece (101), (102), (110), (103) and (112) crystal face.
Fig. 4 is graphene coated Co0.85Se Prussian blue analogue nano square is 100mA/g in current density, and voltage exists
Charge-discharge performance figure within the scope of 0.01-2.6V；As can be seen from Figure 4 graphene coated Co0.85The first charge-discharge of Se
Specific capacity is up to 843mAh/g and 595mAh/g, coulombic efficiency 70.6%.For the first time the larger reason of coulombic efficiency may be because
To form SEI film, the potassium ion in partial electrolyte liquid is consumed.After circulation 10 times, specific capacity is held essentially constant, this and graphite
Alkene large specific surface area, electric conductivity is high, Co0.85The nano square of Se is suitble to the insertion of potassium ion to have very big contact with abjection.
Claims (8)
1. a kind of preparation method for coating Co0.85Se Prussian blue analogue nano square, which comprises the following steps:
S1, cobalt acetate and sodium citrate mixed dissolution are obtained into solution A in deionized water, wherein cobalt acetate and sodium citrate
Mass ratio is 1:(1~2), the mass ratio of cobalt acetate and deionized water is (0.3~0.6): 20；
S2, Cobalt Potassium Cyanide dissolution is obtained into solution B in deionized water, wherein the mass ratio of Cobalt Potassium Cyanide and cobalt acetate
For (1~2): 1；
S3, by solution A be poured into solution B be uniformly mixed, at room temperature stir certain time obtain product C；
S4, product C is successively passed through to centrifuge separation, washing and drying and processing, obtains product D；
S5, it takes product D to be dissolved into the mixed liquor being made of the dispersion liquid of deionized water and graphene and be ultrasonically treated
To solution E；
S6, it sodium selenite is added in solution E is sufficiently mixed, obtain solution F, wherein the mass ratio of sodium selenite and cobalt acetate is
(2~3): 1；
S7, addition hydrazine hydrate obtains Solution H in solution F, wherein the mass ratio of hydrazine hydrate and cobalt acetate is (0.5~1): 2；
S8, Solution H is transferred in reaction kettle, is placed in baking oven and is dried, then natural cooling obtains product at room temperature again
I；
S9, synthetic product I is centrifuged, is washed and drying and processing, obtaining the Co of graphene coated0.85Se Prussian blue analogue
Square.
2. a kind of preparation method for coating Co0.85Se Prussian blue analogue nano square according to claim 1, feature
It is, in S4, the technological parameter of centrifuge separation are as follows: (10000~15000) rpm.
3. a kind of preparation method for coating Co0.85Se Prussian blue analogue nano square according to claim 1, feature
It is, in S5, the mass ratio of deionized water and graphene dispersing solution is (0.003~0.001): 17；Product D and deionized water
Mass ratio is 0.025:17.
4. a kind of preparation method for coating Co0.85Se Prussian blue analogue nano square according to claim 1, feature
Be, in S8, the process conditions of reaction kettle: temperature be 160~200 DEG C, the reaction time be 12~for 24 hours.
5. a kind of preparation method for coating Co0.85Se Prussian blue analogue nano square according to claim 1, feature
It is, in S9, the process conditions of product I centrifuge separation and drying and processing: 10000~15000rpm of eccentricity, 60~80 DEG C of bakings
Dry 12~for 24 hours.
6. a kind of cladding class Co0.85Se Prussian blue analogue nano square, which is characterized in that based on any one of claim 1-5 institute
The preparation method preparation gained stated.
7. a kind of cladding class Co0.85The application of Se Prussian blue analogue nano square, which is characterized in that by stone as claimed in claim 6
Black alkene coats class Co0.85Negative electrode material of the Se Prussian blue analogue nano square as kalium ion battery, is assembled into button cell.
8. a kind of application for coating class Co0.85Se Prussian blue analogue nano square according to claim 7, feature exist
In the specific method for assembling button cell is: cathode uses DMF for solvent, and the formula of pole piece is according to graphene coated class
Co0.85Se Prussian blue analogue nano square: PVDF: acetylene black=9~x:1:x mass ratio is modulated into slurry, then by slurry
It is evenly applied on copper foil, is put into vacuum oven and is dried, obtain experimental cell negative electrode tab by punching later,
In, 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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| CN113593918A (en) * | 2021-07-27 | 2021-11-02 | 陕西君普新航科技有限公司 | Lamellar CoxSelf-assembly preparation method of Se nanosheet array solar cell electrode |
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