CN114400367B - Preparation method of high-energy Al-MOF battery and positive electrode material thereof - Google Patents

Preparation method of high-energy Al-MOF battery and positive electrode material thereof Download PDF

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CN114400367B
CN114400367B CN202210085807.4A CN202210085807A CN114400367B CN 114400367 B CN114400367 B CN 114400367B CN 202210085807 A CN202210085807 A CN 202210085807A CN 114400367 B CN114400367 B CN 114400367B
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王伟
焦树强
郭玉玺
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University of Science and Technology Beijing USTB
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract

The invention discloses a high-energy Al-MOF battery configuration based on a multi-site specific charge storage mechanism and a preparation method of a positive electrode material of the high-energy Al-MOF battery. The invention also provides a multi-site MOF positive electrode material which is synthesized by self-assembly of bipolar organic ligands and active metal ions, and realizes the alternate storage of the opposite charges at multiple sites. The Al-MOF battery prepared by the invention has high specific capacity of 180mAh/g and high energy density of 170Wh/kg, and shows excellent cycling stability.

Description

Preparation method of high-energy Al-MOF battery and positive electrode material thereof
Technical Field
The invention belongs to the technical field of aluminum ion batteries, and particularly relates to a high-energy Al-MOF battery based on a multi-site specific charge storage mechanism and a preparation method of a positive electrode material of the high-energy Al-MOF battery.
Background
Lithium ion batteries have taken the leading position in the market for nearly 30 years due to their high power/energy density. However, the lack of lithium resources and the safety problems of lithium batteries are urgent for the development of new generation energy storage technologies. The rechargeable aluminum ion battery has the advantages of high safety, rich aluminum resources, long cycle life and the like, and has great application potential in the fields of small electronic devices, electric automobiles, large-scale power grid energy storage and the like. In order to ensure reversible dissolution/deposition of aluminum cathodes, existing aluminum ion batteries mostly use room temperature ionic liquids as electrolyte, which contain various aluminum anions and cations. However, these aluminum complex ions have not been fully utilized so far. Conventional cathode materials based on a single type of charge storage mechanism, including graphite-based materials, metal compounds, organic materials, and the like, have approached their performance limits in terms of energy density and cycling stability. Therefore, developing a positive electrode material capable of realizing multi-ion storage is a key to improving the energy density of an aluminum ion battery. In addition, in order to relieve the problem of dissolution of small organic molecules in electrolyte, the cyclic stability of the battery can be effectively improved by preparing the polymer material through a prepolymerization strategy.
Disclosure of Invention
The invention aims to improve the energy density and the cycling stability of an aluminum ion battery, and provides a high-energy Al-MOF battery configuration based on a multi-site specific charge storage mechanism and a preparation method of a positive electrode material of the high-energy Al-MOF battery configuration.
The aim of the invention can be achieved by the following technical scheme:
a high-energy Al-MOF battery based on a multi-site specific charge storage mechanism, wherein the positive electrode is 2D A-MOF or 2D A-MOF/rGO composite material (wherein A is a metal element), the negative electrode is high-purity aluminum foil, and the electrolyte is AlCl 3 /[EMIm]And the diaphragm is a glass fiber.
Preferably, the positive electrode is a 2D A-MOF micrometer sheet or a 2D A-MOF micrometer sheet/rGO composite material.
Preferably, the metal element a is one or more of Cu, co, zn, cd.
Preferably, the electrolyte AlCl 3 /[EMIm]The mol ratio of the Cl ion liquid is 1.3-1.7/1.
Preferably, the preparation method of the positive electrode comprises the following steps: the active material, acetylene black and polyvinylidene fluoride (PVDF) were uniformly mixed in a mass ratio of 6/3/1 in 1-methyl-2-pyrrolidone (NMP), and then the resulting slurry was coated on a tantalum foil current collector, and dried to obtain a positive electrode.
The invention also provides a preparation method of the 2D A-MOF and 2D A-MOF/rGO composite material, which comprises the following steps:
s1: dissolving metal salt, pyrazine and polyvinylpyrrolidone (PVP) in 120mL of a mixed solvent of N, N-Dimethylformamide (DMF) and ethanol to obtain a solution A; the bipolar organic ligand was dissolved in 40mL of a mixed solvent of DMF and ethanol to give solution B.
S2: dropwise adding the solution B obtained in the step S1 into the solution A under stirring, performing ultrasonic treatment on the obtained mixed solution for 10min, transferring into a high-pressure reaction kettle, and reacting at 80 ℃ for 24h. After cooling to room temperature, the purple product was collected by centrifugation for 10min and washed three times with absolute ethanol and dried under vacuum at 60℃for 12h to give 2D A-MOF micro-tablets.
S3: and (3) mixing the 2D A-MOF micrometer sheet obtained in the step (2) with a certain mass of graphene oxide, dissolving the mixture in 150mL of DMF, and carrying out ultrasonic treatment on the obtained suspension for 1h. The suspension was then transferred to an autoclave and reacted at 120℃for 6h. Finally, the mixture was filtered and washed three times with ethanol. Vacuum drying at 60 ℃ for 12h to obtain the 2D A-MOF/rGO composite material.
Preferably, in step S1, the metal salt is copper nitrate trihydrate and the bipolar organic ligand is C 48 H 30 N 4 O 8 。
Preferably, the mass ratio of the metal salt, pyrazine, polyvinylpyrrolidone (PVP) and bipolar organic ligand in step S1 is 4.5:1:25:5.
Preferably, the volume ratio of the mixed solvent DMF and ethanol of the two solutions A and B in the step S1 is 3/1.
Preferably, in the step S3, the mass ratio of the 2D A-MOF micrometer sheet to the graphene oxide is 20 (1-2). The mass of the reduced graphene oxide in the composite material accounts for 5-10% of the mass of the 2D A-MOF micrometer sheet.
The invention has the following beneficial effects:
the invention integrates bipolar organic ligand and active metal ions into MOF framework as aluminum ions by a molecular design methodThe positive electrode material of the sub-battery improves the energy density and the cycling stability of the battery: (1) The two-dimensional microchip structure with high specific surface area is beneficial to the permeation of electrolyte, and the porous layered framework structure allows the reversible intercalation/deintercalation of large-size aluminum complex ions; (2) The multiple redox properties of the bipolar organic ligands allow aluminum complex anions (AlCl) 4 - ) And aluminum complex cation (AlCl) 2 + ) And the high density of active metal sites provides higher storage capacity; (3) The firm MOF framework inhibits the dissolution of small organic molecules in electrolyte, can adapt to the alternate storage of various large-size ions, and improves the cycling stability of the battery. In summary, the Al-MOF battery configuration of the present invention provides an advanced solution for achieving high stability, high energy rechargeable aluminum ion batteries.
Drawings
FIG. 1 is a schematic diagram of the operation principle of the discharging process of an Al-MOF battery;
FIG. 2 is an SEM image of a 2D Cu-MOF positive electrode material for an aluminum ion battery prepared in example 1 of the present invention;
FIG. 3 is a TEM image of a 2D Cu-MOF positive electrode material for an aluminum ion battery prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a 2D Cu-MOF/rGO (5%) composite positive electrode material for an aluminum ion battery prepared in example 1 of the present invention;
fig. 5 is a charge-discharge curve diagram of an aluminum ion battery assembled by a 2D Cu-MOF positive electrode prepared in example 1 of the present invention and a 2D Cu-MOF/rGO composite positive electrode with different reduced graphene oxide contents at a current density of 50 mA/g.
FIG. 6 is a graph showing the charge and discharge curves of the aluminum ion batteries assembled with different metal 2D E-MOF anodes prepared in the comparative example of the present invention at a current density of 50 mA/g.
Detailed Description
The following description is of the preferred embodiments of the present invention, and it should be noted that it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the principle of the invention, and these changes and modifications are also considered to be the scope of the invention.
Example 1
36mg of copper nitrate trihydrate, 8mg of pyrazine and 200mg of polyvinylpyrrolidone (PVP) were dissolved in 120mL of a mixed solvent of N, N-Dimethylformamide (DMF)/absolute ethanol (volume ratio V/V=3/1) to obtain a solution A. 40mg of organic monomer C 48 H 30 N 4 O 8 Solution B was obtained by dissolving in a mixed solvent of 40mL DMF/absolute ethanol (volume ratio V/v=3/1). Solution B was added dropwise to solution a under stirring, and the resulting mixed solution was then sonicated for 10min, then transferred to a autoclave, and reacted at 80 ℃ for 24h. After cooling to room temperature, the purple product was collected by centrifugation for 10min and washed three times with absolute ethanol, and dried under vacuum at 60 ℃ for 12h to give 2D Cu-MOF micro-tablets.
40mg of the 2D Cu-MOF micrometer tablet is taken and respectively mixed with 2mg of graphene oxide and 4mg of graphene oxide to be dissolved in 150mL of DMF, and the obtained suspension is subjected to ultrasonic treatment for 1h. The suspension was then transferred to an autoclave and reacted at 120℃for 6h. Finally, the mixture was filtered and washed three times with ethanol and dried in vacuo at 60 ℃ for 12h to give a 2D Cu-MOF/rGO (5%), 2D Cu-MOF/rGO (10%) composite.
Uniformly mixing the 2D Cu-MOF micrometer sheet and the 2D Cu-MOF/rGO composite material with acetylene black and polyvinylidene fluoride (PVDF) respectively in a mass ratio of 6/3/1 in 1-methyl-2-pyrrolidone (NMP), coating the obtained slurry on a high-purity tantalum foil current collector, and drying to obtain the anode. The obtained positive electrode and aluminum foil negative electrode are subjected to AlCl with the molar ratio of 1.3/1 3 /[EMIm]And assembling the Cl ion liquid electrolyte and the glass fiber diaphragm into the Swagelok type aluminum ion battery or the soft-package aluminum ion battery.
Example 2
36mg of copper nitrate trihydrate, 8mg of pyrazine and 200mg of polyvinylpyrrolidone (PVP) were dissolved in 120mL of a mixed solvent of N, N-Dimethylformamide (DMF)/absolute ethanol (volume ratio V/V=3/1) to obtain a solution A. 40mg of organic monomer C 48 H 30 N 4 O 8 Solution B was obtained by dissolving in a mixed solvent of 40mL DMF/absolute ethanol (volume ratio V/v=3/1). Dropwise adding the solution B to the solution A under stirring, and mixingThe solution was sonicated for 10min and then transferred to an autoclave for reaction at 80℃for 24h. After cooling to room temperature, the purple product was collected by centrifugation for 10min and washed three times with absolute ethanol, and dried under vacuum at 60 ℃ for 12h to give 2D Cu-MOF micro-tablets.
40mg of the 2D Cu-MOF micrometer tablet is taken and respectively mixed with 2mg of graphene oxide and 4mg of graphene oxide to be dissolved in 150mL of DMF, and the obtained suspension is subjected to ultrasonic treatment for 1h. The suspension was then transferred to an autoclave and reacted at 120℃for 6h. Finally, the mixture was filtered and washed three times with ethanol and dried in vacuo at 60 ℃ for 12h to give a 2D Cu-MOF/rGO (5%), 2D Cu-MOF/rGO (10%) composite.
Uniformly mixing the 2D Cu-MOF micrometer sheet and the 2D Cu-MOF/rGO composite material with acetylene black and polyvinylidene fluoride (PVDF) respectively in a mass ratio of 6/3/1 in 1-methyl-2-pyrrolidone (NMP), coating the obtained slurry on a high-purity tantalum foil current collector, and drying to obtain the anode. The obtained positive electrode and aluminum foil negative electrode are subjected to AlCl with the molar ratio of 1.5/1 3 /[EMIm]And assembling the Cl ion liquid electrolyte and the glass fiber diaphragm into the Swagelok type aluminum ion battery or the soft-package aluminum ion battery.
Example 3
36mg of copper nitrate trihydrate, 8mg of pyrazine and 200mg of polyvinylpyrrolidone (PVP) were dissolved in 120mL of a mixed solvent of N, N-Dimethylformamide (DMF)/absolute ethanol (volume ratio V/V=3/1) to obtain a solution A. 40mg of organic monomer C 48 H 30 N 4 O 8 Solution B was obtained by dissolving in a mixed solvent of 40mL DMF/absolute ethanol (volume ratio V/v=3/1). Solution B was added dropwise to solution a under stirring, and the resulting mixed solution was then sonicated for 10min, then transferred to a autoclave, and reacted at 80 ℃ for 24h. After cooling to room temperature, the purple product was collected by centrifugation for 10min and washed three times with absolute ethanol, and dried under vacuum at 60 ℃ for 12h to give 2D Cu-MOF micro-tablets.
40mg of the 2D Cu-MOF micrometer tablet is taken and respectively mixed with 2mg of graphene oxide and 4mg of graphene oxide to be dissolved in 150mL of DMF, and the obtained suspension is subjected to ultrasonic treatment for 1h. The suspension was then transferred to an autoclave and reacted at 120℃for 6h. Finally, the mixture was filtered and washed three times with ethanol and dried in vacuo at 60 ℃ for 12h to give a 2D Cu-MOF/rGO (5%), 2D Cu-MOF/rGO (10%) composite.
Uniformly mixing the 2D Cu-MOF micrometer sheet and the 2D Cu-MOF/rGO composite material with acetylene black and polyvinylidene fluoride (PVDF) respectively in a mass ratio of 6/3/1 in 1-methyl-2-pyrrolidone (NMP), coating the obtained slurry on a high-purity tantalum foil current collector, and drying to obtain the anode. The obtained positive electrode and aluminum foil negative electrode are subjected to AlCl with the molar ratio of 1.7/1 3 /[EMIm]And assembling the Cl ion liquid electrolyte and the glass fiber diaphragm into the Swagelok type aluminum ion battery or the soft-package aluminum ion battery.
Comparative example
The substitution of copper nitrate trihydrate in example 1 for other metal salts produced 2D MOF materials of several different metals. 44mg of cobalt nitrate hexahydrate, or 45mg of zinc nitrate hexahydrate, or 46mg of cadmium nitrate tetrahydrate, respectively, was dissolved in 120mL of a mixed solvent of N, N-Dimethylformamide (DMF)/absolute ethanol (volume ratio V/V=3/1) with 8mg of pyrazine and 200mg of polyvinylpyrrolidone (PVP) to obtain a solution A. 40mg of organic monomer C 48 H 30 N 4 O 8 Solution B was obtained by dissolving in a mixed solvent of 40mL DMF/absolute ethanol (volume ratio V/v=3/1). Solution B was added dropwise to solution a under stirring, and the resulting mixed solution was then sonicated for 10min, then transferred to a autoclave, and reacted at 80 ℃ for 24h. After cooling to room temperature, the purple product was collected by centrifugation for 10min and washed three times with absolute ethanol, and dried under vacuum at 60℃for 12h to give 2D Co-MOF, or 2D Zn-MOF, or 2D Cd-MOF micro-tablets.
Uniformly mixing the 2D Co-MOF, 2D Zn-MOF or 2D Cd-MOF micro-sheets with acetylene black and polyvinylidene fluoride (PVDF) respectively in a mass ratio of 6/3/1 in 1-methyl-2-pyrrolidone (NMP), coating the obtained slurry on a high-purity tantalum foil current collector, and drying to obtain the anode. The obtained positive electrode and aluminum foil negative electrode are subjected to AlCl with the molar ratio of 1.3/1 3 /[EMIm]And assembling the Cl ion liquid electrolyte and the glass fiber diaphragm into the Swagelok type aluminum ion battery or the soft-package aluminum ion battery.
Group in example 1The working principle of the discharging process of the assembled aluminum ion battery is shown in figure 1. It can be seen that the Al-MOF battery has an oxidation reaction (aluminum dissolution) of the aluminum cathode and a reduction reaction of the 2D Cu-MOF cathode during discharge, accompanied by anions (AlCl) 4 - ) Is removed and the subsequent cation (AlCl) 2 + ) Embedding process.
Scanning electron microscopy and transmission electron microscopy were performed on the 2D Cu-MOF micro-sheet and 2D Cu-MOF/rGO (5%) composites of example 1, and the results are shown in fig. 2-4. From fig. 2 and 3, it can be observed that the 2D Cu-MOF ultra-thin micro-sheet structure facilitates the penetration of electrolyte and the exposure of active sites, better capacity. As can be seen from fig. 4, the 2D Cu-MOF is tightly packed by the reduced graphene oxide in the 2D Cu-MOF/rGO (5%) composite material, which is beneficial to improving the electronic conductivity and structural stability of the 2D Cu-MOF.
The 2D Cu-MOF and its composite material in example 1 were used as an aluminum ion battery positive electrode active material, respectively, and the assembled battery was subjected to electrochemical performance test. FIG. 5 is a charge-discharge curve at a current density of 50mA/g, with a 2D Cu-MOF/rGO (5%) composite anode exhibiting optimal electrochemical performance, with two stages of discharge voltage plateau, located around 1.8 and 1.1V, respectively, with a discharge curve similar to that of the 2D Cu-MOF anode, indicating that the capacity contribution is mainly derived from the 2D Cu-MOF. Due to the improvement of electronic conductivity and the optimization of the structure, the 2D Cu-MOF/rGO (5%) composite anode has higher energy density and cycle stability. However, the addition of too much graphene oxide can hinder active ion diffusion, resulting in a lower specific capacity of the 2D Cu-MOF/rGO (10%) composite anode. The discharge specific capacity of the optimized Al-MOF battery is up to 180mAh/g at 50mA/g, the energy density is about 170Wh/kg, and the battery has good cycling stability at high current density.
The assembled batteries were subjected to electrochemical performance tests using the 2D Co-MOF, 2D Zn-MOF, and 2D Cd-MOF of the comparative examples as positive electrode active materials of aluminum ion batteries, respectively. Fig. 6 is a charge-discharge curve of different metal MOF anodes at 50mA/g current density, with the highest energy density compared to other metal MOFs, 2D Cu-MOF and 2D Co-MOF anode assembled aluminum ion batteries, because the high density metal copper and cobalt ions can also act as reactive sites, providing higher specific capacity for 2D MOF materials.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. A high-energy Al-MOF battery based on a multi-site anisotropic charge storage mechanism is characterized by comprising a positive electrode, a negative electrode, an electrolyte and a diaphragm, wherein the positive electrode is a two-dimensional metal organic framework (2D A-MOF) positive electrode or a two-dimensional metal organic framework/reduced graphene oxide (2D A-MOF/rGO) composite positive electrode, the negative electrode is a high-purity aluminum foil, and the electrolyte is aluminum chloride/1-ethyl-3-methylimidazole chloride (AlCl) 3 /[EMIm]Cl) ionic liquid.
2. The multi-site specific charge storage mechanism based high energy Al-MOF cell of claim 1, wherein the metal element a is one or more of Cu, co, zn, cd and the 2D A-MOF is of a microchip structure.
3. The multi-site specific charge storage mechanism based high energy Al-MOF cell of claim 1, wherein the mass of rGO in the 2D A-MOF/rGO composite is 5-10% of the mass of 2D A-MOF.
4. The high energy Al-MOF battery based on a multi-site specific charge storage mechanism of claim 1, wherein the positive electrode preparation method is as follows: the active material, acetylene black and polyvinylidene fluoride (PVDF) were uniformly mixed in a mass ratio of 6/3/1 in 1-methyl-2-pyrrolidone (NMP), and then the resulting slurry was coated on a metal current collector, and dried to obtain the positive electrode.
5. The multi-site specific charge storage mechanism based high energy Al-MOF cell of claim 4, wherein the metal current collector is a high purity tantalum foil.
6. The multi-site specific charge storage mechanism based high energy Al-MOF cell of claim 1, wherein the electrolyte AlCl 3 /[EMIm]The mol ratio of the Cl ion liquid is 1.3-1.7/1.
7. A method for preparing a 2D A-MOF or 2D A-MOF/rGO composite material, comprising the steps of:
s1: dissolving metal salt, pyrazine and polyvinylpyrrolidone (PVP) in a mixed solvent of N, N-Dimethylformamide (DMF) and ethanol to obtain a solution A; dissolving a bipolar organic ligand in a mixed solvent of DMF and ethanol to obtain a solution B;
s2: dropwise adding the solution B obtained in the step S1 into the solution A under stirring, performing ultrasonic treatment on the obtained mixed solution, transferring the mixed solution into a high-pressure reaction kettle, and reacting for 24 hours at 80 ℃; after cooling to room temperature, centrifugally collecting a purple product, washing the purple product with absolute ethyl alcohol, and drying the product in vacuum to obtain a 2D A-MOF micron sheet;
alternatively, S3: mixing the 2D A-MOF micron sheet prepared in the step 2 with graphene oxide with a certain mass, dissolving in DMF (dimethyl formamide), and carrying out ultrasonic treatment on the obtained suspension; and transferring the suspension into a high-pressure reaction kettle, reacting for 6 hours at 120 ℃, washing, and drying to obtain the 2D A-MOF/rGO composite material.
8. The method of manufacturing according to claim 7, wherein: the metal salt in step S1 may be copper nitrate trihydrate, zinc nitrate hexahydrate, cobalt nitrate hexahydrate or cadmium nitrate tetrahydrate, and the bipolar organic ligand is C 48 H 30 N 4 O 8 。
9. The method of manufacturing according to claim 7, wherein: the mass ratio of the metal salt, the pyrazine, the polyvinylpyrrolidone (PVP) and the bipolar organic ligand in the step S1 is 4.5:1:25:5; the volume ratio of the mixed solvent DMF and ethanol of the two solutions A and B in the step S1 is 3/1.
10. The method of manufacturing according to claim 7, wherein: in the step S3, the mass ratio of the 2D A-MOF micrometer sheet to the graphene oxide is 20 (1-2), and the mass of the reduced graphene oxide in the composite material accounts for 5-10% of the mass of the 2D A-MOF micrometer sheet.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105633371A (en) * 2016-01-05 2016-06-01 北京金吕能源科技有限公司 Aluminum-ion secondary battery employing nickel-sulfur compound as positive electrode and preparation technology of aluminum-ion secondary battery
CN108365257A (en) * 2018-02-23 2018-08-03 山东科技大学 A kind of aluminium ion battery and preparation method thereof based on carbon nanotube anode
CN109638304A (en) * 2018-12-29 2019-04-16 江苏大学 A kind of preparation method and purposes of M-MOF-74/ graphene composite cathode material
CN110752356A (en) * 2019-10-15 2020-02-04 肇庆市华师大光电产业研究院 Preparation method of sodium ion battery anode material of double-metal selenide
CN111384387A (en) * 2020-06-01 2020-07-07 杭州德飙新能源设备有限公司 Lithium ion battery and preparation method thereof
WO2021007519A2 (en) * 2019-07-10 2021-01-14 Northwestern University Conductive 2d metal-organic framework for aqueous rechargeable battery cathodes
CN112952047A (en) * 2019-12-10 2021-06-11 中国科学院大连化学物理研究所 Preparation method of carbon-loaded potassium vanadate and application of carbon-loaded potassium vanadate in potassium ion battery
CN113381010A (en) * 2021-05-27 2021-09-10 北京科技大学 Method for preparing Mxenes cathode material for aluminum ion battery in electrochemical one-stop manner
CN113549082A (en) * 2021-07-30 2021-10-26 广东工业大学 Polyhydroxy compound and preparation method and application thereof
CN113964381A (en) * 2021-10-22 2022-01-21 郑州大学 Asymmetric gel-state electrolyte and preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9929435B2 (en) * 2015-02-27 2018-03-27 GM Global Technology Operations LLC Electrolyte structure for metal batteries

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105633371A (en) * 2016-01-05 2016-06-01 北京金吕能源科技有限公司 Aluminum-ion secondary battery employing nickel-sulfur compound as positive electrode and preparation technology of aluminum-ion secondary battery
CN108365257A (en) * 2018-02-23 2018-08-03 山东科技大学 A kind of aluminium ion battery and preparation method thereof based on carbon nanotube anode
CN109638304A (en) * 2018-12-29 2019-04-16 江苏大学 A kind of preparation method and purposes of M-MOF-74/ graphene composite cathode material
WO2021007519A2 (en) * 2019-07-10 2021-01-14 Northwestern University Conductive 2d metal-organic framework for aqueous rechargeable battery cathodes
CN110752356A (en) * 2019-10-15 2020-02-04 肇庆市华师大光电产业研究院 Preparation method of sodium ion battery anode material of double-metal selenide
CN112952047A (en) * 2019-12-10 2021-06-11 中国科学院大连化学物理研究所 Preparation method of carbon-loaded potassium vanadate and application of carbon-loaded potassium vanadate in potassium ion battery
CN111384387A (en) * 2020-06-01 2020-07-07 杭州德飙新能源设备有限公司 Lithium ion battery and preparation method thereof
CN113381010A (en) * 2021-05-27 2021-09-10 北京科技大学 Method for preparing Mxenes cathode material for aluminum ion battery in electrochemical one-stop manner
CN113549082A (en) * 2021-07-30 2021-10-26 广东工业大学 Polyhydroxy compound and preparation method and application thereof
CN113964381A (en) * 2021-10-22 2022-01-21 郑州大学 Asymmetric gel-state electrolyte and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MOFs及其衍生物的制备及电化学性能研究进展;吴凤燕;;云南化工;47(05);18-19 *
有机金属骨架材料在电化学储能领域中的研究进展;陈丹等;化工进展;37(02);628-636 *
球形钴镍双金属有机框架材料的制备及其在超级电容器中的应用;谢樑等;南昌大学学报(工科版);42(03);205-213 *

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