CN116779340B - High-flexibility high-specific-capacity temperature-resistant zinc ion hybrid capacitor and preparation method and application thereof - Google Patents
High-flexibility high-specific-capacity temperature-resistant zinc ion hybrid capacitor and preparation method and application thereof Download PDFInfo
- Publication number
- CN116779340B CN116779340B CN202310755022.8A CN202310755022A CN116779340B CN 116779340 B CN116779340 B CN 116779340B CN 202310755022 A CN202310755022 A CN 202310755022A CN 116779340 B CN116779340 B CN 116779340B
- Authority
- CN
- China
- Prior art keywords
- zinc
- boron
- zinc ion
- nitrogen
- porous carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003990 capacitor Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 71
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000003751 zinc Chemical class 0.000 claims abstract description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 35
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 17
- 239000010432 diamond Substances 0.000 claims abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000151 deposition Methods 0.000 claims description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 25
- 238000003763 carbonization Methods 0.000 claims description 21
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 claims description 20
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 230000008021 deposition Effects 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 12
- 239000011267 electrode slurry Substances 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 10
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical group CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 8
- 239000007774 positive electrode material Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052796 boron Inorganic materials 0.000 abstract description 5
- 239000010405 anode material Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention belongs to the technical field of zinc ion mixed capacitors, and discloses a zinc ion mixed capacitor with high flexibility, high specific capacity and temperature resistance, and a preparation method and application thereof. The zinc ion mixed capacitor provided by the invention takes diamond-boron-nitrogen co-doped layered porous carbon as a main material of an anode, a zinc sheet as a cathode and a gel system containing zinc salt as an electrolyte. According to the invention, boron, nitrogen and diamond are doped on the porous carbon material, so that the porosity of the obtained anode material is improved, the aperture is optimized, the zinc ion mixed capacitor has high specific capacity and cycle stability, and the doping of diamond remarkably improves the temperature resistance and weather resistance of the anode material. Meanwhile, the diamond film is provided with obvious pores, and the uniformity of the pores is high, so that the storage capacity of the positive electrode material to zinc ions is not affected. Solves the problems existing in the prior zinc ion mixed capacitor and can meet the application of the zinc ion mixed capacitor with higher performance.
Description
Technical Field
The invention relates to the technical field of zinc ion hybrid capacitors, in particular to a high-flexibility high-specific-capacity temperature-resistant zinc ion hybrid capacitor, and a preparation method and application thereof.
Background
The hybrid capacitor combines the high energy density of the battery with the high power density of the supercapacitor, and is a novel energy storage device with excellent electrochemical performance. The zinc ion mixed capacitor has high theoretical capacity (823 mAh/g), low oxidation-reduction voltage (-0.76V), rich zinc source, low cost, no pollution and high safety compared with lithium ion, sodium ion and potassium ion, and has recently been paid attention by researchers.
Currently, in zinc ion hybrid capacitors, a porous carbon material is generally used as a positive electrode material. The porous carbon material prepared by taking the metal organic framework material as a template has high specific surface area, porosity and stability, and is considered to be an effective energy storage material of the hybrid capacitor. In order to further meet the electrochemical performance requirement of the zinc ion hybrid capacitor, a metal organic framework material is generally subjected to load modification to obtain a porous carbon material. However, the existing porous carbon material has a plurality of problems, such as uneven pore size and uneven pore distribution of the porous carbon material, which cause low zinc ion storage capacity and further cause non-ideal electrochemical performance of the zinc ion capacitor; in order to increase the porosity, a large amount of strong acid and strong alkali are used in the preparation process, the process is complicated and the environment is polluted; poor temperature resistance and weather resistance, and can not adapt to complex environments.
Therefore, there is a need in the art to develop a zinc ion hybrid capacitor that has high flexibility, high specific capacity and temperature resistance.
Disclosure of Invention
The invention aims to provide a zinc ion mixed capacitor with high flexibility, high specific capacity and temperature resistance, and a preparation method and application thereof, so as to solve the problems of poor electrochemical performance, complex preparation process, environmental pollution, poor temperature resistance and weather resistance of the traditional zinc ion mixed capacitor.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a zinc ion mixed capacitor with high flexibility, high specific capacity and temperature resistance, which comprises an anode, a cathode and an electrolyte; the positive electrode comprises diamond-boron-nitrogen co-doped layered porous carbon, a conductive agent and a binder; the negative electrode is a zinc sheet; the electrolyte is a gel system containing zinc salt.
Preferably, the preparation method of the diamond-boron-nitrogen co-doped layered porous carbon comprises the following steps:
(1) Mixing 2-methylimidazole, zinc acetate and water, and sequentially aging and centrifuging to obtain a carbon source;
(2) Mixing a carbon source with ammonium borate, and carbonizing to obtain boron-nitrogen doped porous carbon;
(3) And depositing a diamond film on the surface of the boron-nitrogen doped porous carbon, and calcining to obtain the diamond-boron-nitrogen co-doped layered porous carbon.
Preferably, the mass volume ratio of the 2-methylimidazole to the zinc acetate to the water is 3-4 g to 1g to 20-30 mL; the aging time is 1-2 h; the rotational speed of the centrifugation is 1000-2000 r/min, and the centrifugation time is 30-50 min.
Preferably, the mass ratio of the carbon source to the ammonium borate is 1:2-6; the carbonization is performed under argon; the carbonization temperature is 800-900 ℃, the carbonization heating rate is 3-5 ℃/min, and the carbonization heat preservation time is 2-3 h.
Preferably, the deposition is performed under a hydrogen atmosphere; the carbon sources used for the deposition are methane, ethanol and anisole; the volume ratio of the methane to the ethanol to the anisole is 3-4:0.5-1:0.2-0.5; the flow rate of the carbon source is 30-40 sccm; during deposition, the surface temperature of the boron-nitrogen doped porous carbon is 700-800 ℃; the deposition air pressure is 5-7 kPa, and the deposition time is 0.5-2 hours; the calcining temperature is 700-800 ℃, and the calcining time is 0.5-1 h.
Preferably, the conductive agent is conductive carbon black, conductive graphite or carbon nanotubes; the binder is carboxymethyl cellulose.
Preferably, the preparation of the zinc salt-containing gel system comprises the following steps: reacting zinc salt solution, monomer, cross-linking agent and initiator to obtain gel system containing zinc salt; the zinc salt solution is a zinc salt aqueous solution; the concentration of the zinc salt solution is 0.5-0.75 g/mL; the zinc salt in the zinc salt solution is zinc sulfate, zinc nitrate or zinc chloride; the monomer is 2-acrylamide-2-methylpropanesulfonic acid; the cross-linking agent is diisocyanate; the initiator is ammonium persulfate; the mass ratio of zinc salt, monomer, cross-linking agent and initiator is 20-30:2-3:0.01-0.03:0.2-0.4; the reaction time is 10-20 min.
The invention also provides a preparation method of the zinc ion mixed capacitor with high flexibility, high specific capacity and temperature resistance, which comprises the following steps:
1) Mixing diamond-boron-nitrogen co-doped layered porous carbon, a conductive agent, a binder and a solvent to obtain electrode slurry, and coating the electrode slurry on a current collector to obtain an anode;
2) And sequentially assembling the negative electrode, the electrolyte and the positive electrode, and then curing to obtain the zinc ion mixed capacitor.
Preferably, the solvent is N-methylpyrrolidone; the mass volume ratio of the diamond-boron-nitrogen co-doped layered porous carbon, the conductive agent, the binder and the solvent is 7-8 g:1-2 g:1g: 10-20 mL; the thickness of the coating is 30-60 mu m; the curing time is 1-2 h.
The invention also provides application of the zinc ion mixed capacitor with high flexibility, high specific capacity and temperature resistance in electronic equipment.
Compared with the prior art, the invention has the following beneficial effects:
(1) Boron and nitrogen are doped on a porous carbon material to obtain a positive electrode material; the porosity of the obtained positive electrode material is improved, the aperture is optimized, the aperture is more uniform, the storage capacity of the positive electrode material to zinc ions is greatly improved, and the zinc ion mixed capacitor has high specific capacity and cycle stability. The obtained zinc ion mixed capacitor can provide specific capacity of 228-230 mAh/g, and has capacity retention rate of more than 97.5% after 10000 times of circulation;
(2) According to the invention, the diamond film is loaded on the porous carbon material doped with boron and nitrogen, so that the temperature resistance and weather resistance of the anode material are remarkably improved. Meanwhile, the diamond film is provided with obvious pores, so that the uniformity of the pores is high, and the storage capacity of the positive electrode material to zinc ions is not affected;
(3) The preparation process is simple, strong acid and strong alkali are not needed, and the preparation method belongs to a green environment-friendly material.
Detailed Description
The invention provides a zinc ion mixed capacitor with high flexibility, high specific capacity and temperature resistance, which comprises an anode, a cathode and an electrolyte; the positive electrode comprises diamond-boron-nitrogen co-doped layered porous carbon, a conductive agent and a binder; the negative electrode is a zinc sheet; the electrolyte is a gel system containing zinc salt.
In the invention, the preparation method of the diamond-boron-nitrogen co-doped layered porous carbon comprises the following steps:
(1) Mixing 2-methylimidazole, zinc acetate and water, and sequentially aging and centrifuging to obtain a carbon source;
(2) Mixing a carbon source with ammonium borate, and carbonizing to obtain boron-nitrogen doped porous carbon;
(3) And depositing a diamond film on the surface of the boron-nitrogen doped porous carbon, and calcining to obtain the diamond-boron-nitrogen co-doped layered porous carbon.
In the preparation step (1) of the diamond-boron-nitrogen co-doped layered porous carbon, the mass volume ratio of the 2-methylimidazole to the zinc acetate to the water is preferably 3-4 g to 1g to 20-30 mL, and more preferably 3.2-3.8 g to 1g to 22-26 mL; the ageing is carried out under the condition of stirring; the stirring speed is preferably 500-800 r/min, and more preferably 600-700 r/min; the aging time is preferably 1 to 2 hours, more preferably 1.5 hours; the rotation speed of the centrifugation is preferably 1000-2000 r/min, and more preferably 1200-1500 r/min; the time for centrifugation is preferably 30 to 50 minutes, more preferably 40 to 45 minutes.
In the preparation step (1) of the diamond-boron-nitrogen co-doped layered porous carbon, after centrifugation is finished, washing and drying the obtained precipitate in sequence; the reagent used for washing is water; the number of times of the washing is preferably 2 to 4 times, more preferably 3 times; the temperature of the drying is preferably 80-100 ℃, and more preferably 90-95 ℃; the drying time is preferably 30 to 50 minutes, more preferably 35 to 40 minutes.
In the preparation step (2) of the diamond-boron-nitrogen co-doped layered porous carbon, the mass ratio of the carbon source to the ammonium borate is preferably 1:2-6, and more preferably 1:3-4; the carbonization is performed under argon; the carbonization temperature is preferably 800-900 ℃, and more preferably 810-850 ℃; the heating rate of carbonization is preferably 3-5 ℃/min, more preferably 4 ℃/min; the holding time for carbonization is preferably 2 to 3 hours, more preferably 130 to 150 minutes.
In the preparation step (2) of the diamond-boron-nitrogen co-doped layered porous carbon, after carbonization is finished, the obtained product is sequentially subjected to standing, washing and drying; the time for the standing is preferably 4 to 6 hours, more preferably 5 to 5.5 hours; the reagent used for washing is water; the number of times of the washing is preferably 2 to 4 times, more preferably 3 times; the temperature of the drying is preferably 80-100 ℃, and more preferably 90-95 ℃; the drying time is preferably 30 to 50 minutes, more preferably 35 to 40 minutes.
In the preparation step (3) of the diamond-boron-nitrogen co-doped layered porous carbon, the deposition is performed under a hydrogen atmosphere; the flow rate of the hydrogen gas is preferably 20 to 30sccm, more preferably 25 to 28sccm; the carbon source used for the deposition is preferably methane, ethanol and anisole; the volume ratio of the methane, the ethanol and the anisole is preferably 3-4:0.5-1:0.2-0.5, and more preferably 3.5-3.8:0.6-0.9:0.3-0.4; the flow rate of the carbon source is preferably 30 to 40sccm, more preferably 32 to 35sccm; during deposition, the surface temperature of the boron-nitrogen doped porous carbon is preferably 700-800 ℃, and more preferably 750-780 ℃; the gas pressure for the deposition is preferably 5 to 7kPa, more preferably 6kPa; the deposition time is preferably 0.5 to 2 hours, more preferably 1 to 1.5 hours; the temperature of the calcination is preferably 700 to 800 ℃, and more preferably 750 to 780 ℃; the calcination time is preferably 0.5 to 1 hour, more preferably 40 to 50 minutes.
In the deposition process of the diamond film, under the action of hydrogen, methane is generated into CH 3 And H, ethanol to CH 3 、CH 2 And OH, anisole to form CH 3 And O, most of which is CH 3 Forming diamond phase, CH 2 And a small part CH 3 The non-diamond phase is formed, the generated H and O are etched to a certain extent, and the formed diamond film has a uniform pore structure through subsequent calcination.
In the carbonization process, metallic zinc in zinc acetate is evaporated at high temperature to form a rich micropore structure, so that boron-nitrogen doped porous carbon obtains a large specific surface area, the subsequent step of pickling to remove zinc can be omitted, the cost is saved, and the pollution to the environment is avoided. The synergistic effect of boron and nitrogen double doping is adopted, so that the active sites of the reaction are increased, and the electrochemical kinetics and specific capacity of the carbon material are improved. Besides providing a boron source and a nitrogen source, the ammonium borate is also used as a pore-forming agent, and can be decomposed to release ammonia gas in the carbonization process, so that the pore structure is optimized, the storage capacity of zinc ions is improved, and the electrochemical performance of the obtained zinc ion hybrid capacitor is further improved; meanwhile, the diamond film formed by deposition can obviously improve the temperature resistance and weather resistance of the obtained boron-nitrogen doped porous carbon, and the diamond film is provided with obvious fine holes, so that the uniformity of the holes is high, and the storage capacity of the anode material to zinc ions is not affected.
In the present invention, the conductive agent is preferably conductive carbon black, conductive graphite or carbon nanotubes; the particle diameter of the conductive carbon black is preferably 20 to 40nm, more preferably 30 to 35nm; the particle diameter of the conductive graphite is preferably 5 to 10. Mu.m, more preferably 7 to 9. Mu.m; the diameter of the carbon nanotubes is preferably 20 to 40nm, more preferably 30 to 35nm; the length of the carbon nanotubes is preferably 5 to 15. Mu.m, more preferably 8 to 12. Mu.m; the binder is preferably carboxymethyl cellulose.
In the present invention, the preparation of the zinc salt-containing gel system comprises the following steps: and (3) reacting the zinc salt solution, the monomer, the cross-linking agent and the initiator to obtain a gel system containing zinc salt.
In the step of preparing the zinc salt-containing gel system, the zinc salt solution is preferably an aqueous solution of zinc salt; the concentration of the zinc salt solution is preferably 0.5 to 0.75g/mL, more preferably 0.6 to 0.7g/mL; the zinc salt in the zinc salt solution is preferably zinc sulfate, zinc nitrate or zinc chloride; the monomer is preferably 2-acrylamide-2-methylpropanesulfonic acid; the crosslinker is preferably a diisocyanate; the initiator is preferably ammonium persulfate; the mass ratio of the zinc salt to the monomer to the cross-linking agent to the initiator is preferably 20-30:2-3:0.01-0.03:0.2-0.4, and more preferably 23-26:2.1-2.5:0.02:0.3-0.35; the reaction time is preferably 10 to 20 minutes, more preferably 12 to 15 minutes.
The invention also provides a preparation method of the zinc ion mixed capacitor with high flexibility, high specific capacity and temperature resistance, which comprises the following steps:
1) Mixing diamond-boron-nitrogen co-doped layered porous carbon, a conductive agent, a binder and a solvent to obtain electrode slurry, and coating the electrode slurry on a current collector to obtain an anode;
2) And sequentially assembling the negative electrode, the electrolyte and the positive electrode, and then curing to obtain the zinc ion mixed capacitor.
In the preparation step 1) of the zinc ion mixed capacitor, the solvent is preferably N-methylpyrrolidone; the mass volume ratio of the diamond-boron-nitrogen co-doped layered porous carbon, the conductive agent, the binder and the solvent is preferably 7-8 g:1-2 g:1g:10 to 20mL, more preferably 7.2 to 7.6g:1.5 to 1.8g:1g: 11-18 mL; the current collector is preferably aluminum foil; the thickness of the current collector is preferably 10 to 15 μm, more preferably 12 to 14 μm; the thickness of the coating is preferably 30 to 60. Mu.m, more preferably 40 to 50. Mu.m.
In the preparation step 1) of the zinc ion mixed capacitor, after the coating is completed, vacuum drying is carried out on the obtained product; the vacuum degree of the vacuum drying is preferably-0.02 to-0.01 MPa, and more preferably-0.015 MPa; the temperature of the vacuum drying is preferably 80-100 ℃, and more preferably 90-95 ℃; the time for the vacuum drying is preferably 30 to 50 minutes, more preferably 40 to 45 minutes.
In the preparation step 2) of the zinc ion mixed capacitor, the curing time is preferably 1 to 2 hours, more preferably 1.5 hours.
The invention also provides application of the zinc ion mixed capacitor with high flexibility, high specific capacity and temperature resistance in electronic equipment.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparation of diamond-boron-nitrogen co-doped layered porous carbon:
mixing 6g of 2-methylimidazole, 2g of zinc acetate and 40mL of water, aging for 1h at a stirring rate of 500r/min, centrifuging at a rotating speed of 1000r/min for 30min after aging, washing the centrifuged precipitate with water for 3 times, and drying at 80 ℃ for 30min to obtain a carbon source; mixing 3g of carbon source and 6g of ammonium borate, placing the mixture in a carbonization box, heating to 800 ℃ at a heating rate of 3 ℃/min under the protection of argon, preserving heat for 2 hours at 800 ℃ for carbonization, taking out a carbonized product, standing for 6 hours, washing with water for 3 times, and drying at 80 ℃ for 30 minutes to obtain boron-nitrogen doped porous carbon; placing boron-nitrogen doped porous carbon in a reaction chamber of a chemical vapor deposition device, keeping the surface temperature of the boron-nitrogen doped porous carbon at 750 ℃, introducing hydrogen at a flow rate of 28sccm (continuously introducing hydrogen in the deposition process), introducing mixed gas of methane, ethanol and anisole with a volume ratio of 3:0.5:0.2 at a flow rate of 30sccm after 10min, depositing for 1h to obtain a diamond film, keeping the deposited air pressure at 5kPa, calcining the product at 750 ℃ for 1h after the deposition is finished to obtain diamond-boron-nitrogen co-doped layered porous carbon;
7.2g of the obtained diamond-boron-nitrogen co-doped layered porous carbon, 1.5g of conductive carbon black with the particle size of 30nm, 1g of carboxymethyl cellulose and 20 mLN-methyl pyrrolidone are mixed to obtain electrode slurry; uniformly coating electrode slurry on aluminum foil with the size of 3cm multiplied by 2cm and the thickness of 10 mu m, wherein the thickness of the coating is 35 mu m, and after the coating is finished, placing the whole body in a vacuum drying oven, and vacuum drying at-0.02 MPa and 90 ℃ for 30min to obtain a positive electrode;
20g of zinc sulfate is dissolved in 40mL of water, and 2g of 2-acrylamide-2-methylpropanesulfonic acid, 0.02g of diisocyanate and 0.2g of ammonium persulfate are added to react for 10min to obtain a gel system containing zinc salt;
and sequentially assembling a zinc sheet with the size of 3cm multiplied by 2cm, a gel system containing zinc salt and a positive electrode, then solidifying for 1h at room temperature, and packaging to obtain the zinc ion mixed capacitor.
The zinc ion mixed capacitor obtained in the embodiment has a capacity retention rate of 97.5% after 10000 times of circulation; the capacity retention of the zinc ion mixed capacitor obtained in this example after 1000 cycles at-15℃was 76.3%.
Example 2
Preparation of diamond-boron-nitrogen co-doped layered porous carbon:
mixing 4g of 2-methylimidazole, 1g of zinc acetate and 30mL of water, aging for 1.5h at a stirring rate of 800r/min, centrifuging at a rotating speed of 1500r/min for 40min after aging, washing the centrifuged precipitate with water for 3 times, and drying at 80 ℃ for 35min to obtain a carbon source; mixing 2g of carbon source and 8g of ammonium borate, placing the mixture in a carbonization box, heating to 850 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving heat for 2 hours at 850 ℃ for carbonization, taking out and standing a carbonized product, washing with water for 3 times, and drying at 80 ℃ for 30 minutes to obtain boron-nitrogen doped porous carbon; placing boron-nitrogen doped porous carbon in a reaction chamber of a chemical vapor deposition device, keeping the surface temperature of the boron-nitrogen doped porous carbon at 800 ℃, introducing hydrogen at a flow rate of 26sccm (continuously introducing hydrogen in the deposition process), introducing mixed gas of methane, ethanol and anisole at a volume ratio of 3:0.5:0.2 at a flow rate of 40sccm after 10min, depositing for 1h to obtain a diamond film, keeping the deposited air pressure at 5kPa, calcining the product at 800 ℃ for 1h after the deposition is finished to obtain the diamond-boron-nitrogen co-doped layered porous carbon;
mixing 7.8g of the obtained diamond-boron-nitrogen co-doped layered porous carbon, 1g of conductive graphite with the particle size of 8 mu m, 1g of carboxymethyl cellulose and 18 mLN-methylpyrrolidone to obtain electrode slurry; uniformly coating electrode slurry on aluminum foil with the size of 3cm multiplied by 2cm and the thickness of 15 mu m, wherein the thickness of the coating is 40 mu m, and after the coating is finished, placing the whole body in a vacuum drying oven, and vacuum drying at-0.02 MPa and 90 ℃ for 30min to obtain a positive electrode;
30g of zinc sulfate is dissolved in 40mL of water, and 2.5g of 2-acrylamide-2-methylpropanesulfonic acid, 0.03g of diisocyanate and 0.3g of ammonium persulfate are added to react for 15min to obtain a gel system containing zinc salt;
and sequentially assembling a zinc sheet with the size of 3cm multiplied by 2cm, a gel system containing zinc salt and a positive electrode, then solidifying for 1h at room temperature, and packaging to obtain the zinc ion mixed capacitor.
The zinc ion mixed capacitor obtained in the embodiment has a capacity retention rate of 97.6% after 10000 times of circulation; the capacity retention rate of the zinc ion mixed capacitor obtained in this example after 1000 cycles at-15℃was 80.5%.
Example 3
Preparation of diamond-boron-nitrogen co-doped layered porous carbon:
mixing 7g of 2-methylimidazole, 2g of zinc acetate and 40mL of water, aging for 2 hours at a stirring rate of 600r/min, centrifuging at a rotating speed of 1800r/min for 30min after aging, washing the centrifuged precipitate with water for 3 times, and drying at 90 ℃ for 40min to obtain a carbon source; mixing 1g of carbon source and 5g of ammonium borate, placing the mixture in a carbonization box, heating to 880 ℃ at a heating rate of 4 ℃/min under the protection of argon, preserving heat for 2.5 hours at 880 ℃ for carbonization, taking out a carbonized product, standing for 6 hours, washing with water for 3 times, and drying at 90 ℃ for 30 minutes to obtain boron-nitrogen doped porous carbon; placing boron-nitrogen doped porous carbon in a reaction chamber of a chemical vapor deposition device, keeping the surface temperature of the boron-nitrogen doped porous carbon at 780 ℃, introducing hydrogen at a flow rate of 30sccm (continuously introducing hydrogen in the deposition process), introducing mixed gas of methane, ethanol and anisole at a volume ratio of 3.5:0.8:0.4 at a flow rate of 35sccm after 10min, depositing for 2h to obtain a diamond film, keeping the deposited air pressure at 5kPa, calcining the product at 800 ℃ for 1h after the deposition is finished to obtain the diamond-boron-nitrogen co-doped layered porous carbon;
mixing 7.5g of the obtained diamond-boron-nitrogen co-doped layered porous carbon, 1.5g of carbon nanotubes with the diameter of 30nm and the length of 12 mu m, 1g of carboxymethyl cellulose and 12 mLN-methyl pyrrolidone to obtain electrode slurry; uniformly coating electrode slurry on aluminum foil with the size of 3cm multiplied by 2cm and the thickness of 10 mu m, wherein the thickness of the coating is 50 mu m, and after the coating is finished, placing the whole body in a vacuum drying oven, and vacuum drying at-0.02 MPa and 90 ℃ for 30min to obtain a positive electrode;
25g of zinc sulfate is dissolved in 40mL of water, 3g of 2-acrylamide-2-methylpropanesulfonic acid, 0.01g of diisocyanate and 0.25g of ammonium persulfate are added for reaction for 10min, and a gel system containing zinc salt is obtained;
and sequentially assembling a zinc sheet with the size of 3cm multiplied by 2cm, a gel system containing zinc salt and a positive electrode, then solidifying for 1h at room temperature, and packaging to obtain the zinc ion mixed capacitor.
The zinc ion mixed capacitor obtained in the embodiment has a capacity retention rate of 97.5% after 10000 times of circulation; the capacity retention rate of the zinc ion mixed capacitor obtained in this example after 1000 cycles at-15℃was 72.5%.
The energy storage effect of the zinc ion hybrid capacitors obtained in examples 1 to 3 was examined, and the test method and results were as follows:
the testing method comprises the following steps: the specific capacities obtained by charging and discharging with current densities of 0.1A/g, 2A/g, 5A/g, 10A/g, and 20A/g, respectively, are shown in Table 1.
Table 1 specific capacities of zinc ion mixed capacitors obtained in examples 1 to 3
As can be seen from Table 1, the zinc ion mixed capacitor obtained by the present invention can provide a specific capacity of 228 to 230mAh/g, and can maintain a high specific capacity of 85 to 94mAh/g even at a current density of 20A/g.
As is clear from examples 1 to 3 and Table 1, the zinc ion mixed capacitor obtained in the present invention has high specific capacity, excellent cycle performance and excellent temperature and weather resistance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A zinc ion mixed capacitor with high flexibility, high specific capacity and temperature resistance, which is characterized by comprising a positive electrode, a negative electrode and an electrolyte; the positive electrode comprises diamond-boron-nitrogen co-doped layered porous carbon, a conductive agent and a binder; the negative electrode is a zinc sheet; the electrolyte is a gel system containing zinc salt;
the preparation method of the diamond-boron-nitrogen co-doped layered porous carbon comprises the following steps:
(1) Mixing 2-methylimidazole, zinc acetate and water, and sequentially aging and centrifuging to obtain a carbon source;
(2) Mixing a carbon source with ammonium borate, and carbonizing to obtain boron-nitrogen doped porous carbon;
(3) Depositing a diamond film on the surface of the boron-nitrogen doped porous carbon, and calcining to obtain the diamond-boron-nitrogen co-doped layered porous carbon;
the deposition is performed under a hydrogen atmosphere; the carbon sources used for the deposition are methane, ethanol and anisole; the volume ratio of the methane to the ethanol to the anisole is 3-4:0.5-1:0.2-0.5; the flow rate of the carbon source is 30-40 sccm; during deposition, the surface temperature of the boron-nitrogen doped porous carbon is 700-800 ℃; the deposition air pressure is 5-7 kPa, and the deposition time is 0.5-2 hours; the calcining temperature is 700-800 ℃, and the calcining time is 0.5-1 h.
2. The zinc ion mixed capacitor with high flexibility, high specific capacity and temperature resistance according to claim 1, wherein the mass volume ratio of the 2-methylimidazole to the zinc acetate to the water is 3-4 g/1 g/20-30 mL; the aging time is 1-2 h; the rotational speed of the centrifugation is 1000-2000 r/min, and the centrifugation time is 30-50 min.
3. The zinc ion mixed capacitor with high flexibility, high specific capacity and temperature resistance according to claim 1 or 2, wherein the mass ratio of the carbon source to the ammonium borate is 1:2-6; the carbonization is performed under argon; the carbonization temperature is 800-900 ℃, the carbonization heating rate is 3-5 ℃/min, and the carbonization heat preservation time is 2-3 h.
4. The high-flexibility high-specific-capacity and temperature-resistant zinc ion hybrid capacitor according to claim 1, wherein the conductive agent is conductive carbon black, conductive graphite or carbon nanotubes; the binder is carboxymethyl cellulose.
5. The high flexibility high specific capacity and temperature resistant zinc ion hybrid capacitor according to claim 4, wherein the preparation of the zinc salt containing gel system comprises the steps of: reacting zinc salt solution, monomer, cross-linking agent and initiator to obtain gel system containing zinc salt; the zinc salt solution is a zinc salt aqueous solution; the concentration of the zinc salt solution is 0.5-0.75 g/mL; the zinc salt in the zinc salt solution is zinc sulfate, zinc nitrate or zinc chloride; the monomer is 2-acrylamide-2-methylpropanesulfonic acid; the cross-linking agent is diisocyanate; the initiator is ammonium persulfate; the mass ratio of zinc salt, monomer, cross-linking agent and initiator is 20-30:2-3:0.01-0.03:0.2-0.4; the reaction time is 10-20 min.
6. The method for manufacturing a zinc ion mixed capacitor with high flexibility, high specific capacity and temperature resistance according to any one of claims 1 to 5, comprising the steps of:
1) Mixing diamond-boron-nitrogen co-doped layered porous carbon, a conductive agent, a binder and a solvent to obtain electrode slurry, and coating the electrode slurry on a current collector to obtain an anode;
2) And sequentially assembling the negative electrode, the electrolyte and the positive electrode, and then curing to obtain the zinc ion mixed capacitor.
7. The method for preparing a zinc ion mixed capacitor with high flexibility, high specific capacity and temperature resistance according to claim 6, wherein the solvent is N-methylpyrrolidone; the mass volume ratio of the diamond-boron-nitrogen co-doped layered porous carbon, the conductive agent, the binder and the solvent is 7-8 g:1-2 g:1g: 10-20 mL; the thickness of the coating is 30-60 mu m; the curing time is 1-2 h.
8. Use of the zinc ion mixed capacitor with high flexibility, high specific capacity and temperature resistance in electronic equipment according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310755022.8A CN116779340B (en) | 2023-06-26 | 2023-06-26 | High-flexibility high-specific-capacity temperature-resistant zinc ion hybrid capacitor and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310755022.8A CN116779340B (en) | 2023-06-26 | 2023-06-26 | High-flexibility high-specific-capacity temperature-resistant zinc ion hybrid capacitor and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116779340A CN116779340A (en) | 2023-09-19 |
| CN116779340B true CN116779340B (en) | 2024-02-06 |
Family
ID=88006002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310755022.8A Active CN116779340B (en) | 2023-06-26 | 2023-06-26 | High-flexibility high-specific-capacity temperature-resistant zinc ion hybrid capacitor and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116779340B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118116747B (en) * | 2024-04-30 | 2024-06-25 | 国容智能科技(南京)有限公司 | Wide-temperature-range water system zinc ion hybrid supercapacitor based on metal organic framework material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191204A (en) * | 2006-12-22 | 2008-06-04 | 上海电机学院 | Method for preparing network interpenetration type diamond coat multi-pore electrode |
| CN107010624A (en) * | 2017-04-24 | 2017-08-04 | 安徽大学 | Nitrogen and boron doped porous carbon for supercapacitor electrode and preparation method thereof |
| CN110993358A (en) * | 2019-12-24 | 2020-04-10 | 合肥国轩高科动力能源有限公司 | Flexible zinc ion capacitor |
| CN113493196A (en) * | 2021-07-20 | 2021-10-12 | 北方民族大学 | Boron-nitrogen co-doped porous carbon material and preparation method and application thereof |
-
2023
- 2023-06-26 CN CN202310755022.8A patent/CN116779340B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191204A (en) * | 2006-12-22 | 2008-06-04 | 上海电机学院 | Method for preparing network interpenetration type diamond coat multi-pore electrode |
| CN107010624A (en) * | 2017-04-24 | 2017-08-04 | 安徽大学 | Nitrogen and boron doped porous carbon for supercapacitor electrode and preparation method thereof |
| CN110993358A (en) * | 2019-12-24 | 2020-04-10 | 合肥国轩高科动力能源有限公司 | Flexible zinc ion capacitor |
| CN113493196A (en) * | 2021-07-20 | 2021-10-12 | 北方民族大学 | Boron-nitrogen co-doped porous carbon material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116779340A (en) | 2023-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN116779340B (en) | High-flexibility high-specific-capacity temperature-resistant zinc ion hybrid capacitor and preparation method and application thereof | |
| CN112652749B (en) | Carbon cloth with uniformly distributed cobalt particles and vertical graphene growing thereon and preparation method and application thereof | |
| CN112850708A (en) | Preparation method and application of nitrogen-doped porous carbon material with high specific surface area | |
| GB2618729A (en) | Preparation method of hard carbon anode material and use thereof | |
| CN112239201A (en) | Method for preparing nitrogen-sulfur double-doped porous carbon through one-step carbonization | |
| CN116169260A (en) | β”-Al 2 O 3 And N-doped C composite coated Na 3 V 2 (PO 4 ) 2 F 3 Electrode material | |
| CN111403659A (en) | Ultrahigh-specific-surface-area carbon aerogel coating diaphragm intermediate layer for lithium-sulfur battery, preparation method of ultrahigh-specific-surface-area carbon aerogel coating diaphragm intermediate layer and lithium-sulfur battery | |
| CN112299389A (en) | Method for preparing sodium ion carbon negative electrode material by using nitrogen-doped porous biomass carbon | |
| CN114497893A (en) | Diaphragm based on high-nitrogen-doped carbon composite graphene material and preparation method and application thereof | |
| CN114678494A (en) | Method for pre-lithiating negative electrode and simultaneously obtaining SEI (solid electrolyte interface) film, negative electrode and lithium ion battery | |
| CN113871792A (en) | Folded molybdenum disulfide composite diaphragm for lithium-sulfur battery and preparation method thereof | |
| CN115676802B (en) | Hard carbon negative electrode material of sodium ion battery and preparation method thereof | |
| CN115411260B (en) | Gas phase modification method of Prussian blue type sodium electric anode material and anode material prepared by same | |
| US20240178371A1 (en) | Silicon-based anode material with high stability and conductivity for lithium-ion batteries and preparation method thereof | |
| CN115020654B (en) | Preparation method of hard carbon composite material for sodium ion battery | |
| CN117712360B (en) | Preparation method of composite modified graphite anode material | |
| CN118136787B (en) | Method for preparing sodium ion battery negative electrode by bamboo wood and sodium ion battery negative electrode | |
| CN116200149B (en) | Preparation process of functionalized graphene adhesive for negative electrode of lead-carbon battery | |
| CN118108211B (en) | Phosphorus-doped hard carbon negative electrode material, preparation method thereof and vehicle | |
| CN117430824B (en) | Nitrogen-doped hollow MOF material and preparation method and application thereof | |
| CN116253308B (en) | Bowl-shaped carbon network anode material and preparation method thereof | |
| CN117525372B (en) | Lithium battery anode material based on metal organic framework material | |
| CN117894959A (en) | Active carbon negative electrode material for sodium ion battery and preparation method thereof | |
| CN116885296A (en) | Graphene-based water-based zinc-iodine secondary battery and preparation method thereof | |
| CN116525317A (en) | Boron-nitrogen co-doped dodecahedron layered porous carbon, preparation method thereof and layered porous carbon electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |