CN113078312A - Bismuth chloride @ porous carbon composite chloride ion battery positive electrode material and preparation method thereof - Google Patents
Bismuth chloride @ porous carbon composite chloride ion battery positive electrode material and preparation method thereof Download PDFInfo
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- CN113078312A CN113078312A CN202110328511.6A CN202110328511A CN113078312A CN 113078312 A CN113078312 A CN 113078312A CN 202110328511 A CN202110328511 A CN 202110328511A CN 113078312 A CN113078312 A CN 113078312A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a bismuth chloride @ porous carbon composite chloride ion battery positive electrode material and a preparation method thereof, wherein the preparation process comprises the following steps: adding a certain amount of BiCl3Dissolving in hydrochloric acid; then the obtained BiCl is added3Uniformly mixing the solution with a certain amount of porous carbon material, wherein the total pore volume of the porous carbon is more than or equal to the volume of the added hydrochloric acid; then standing the obtained mixture for at least 12h under a vacuum environment; finally, carrying out rotary evaporation on the obtained mixture for 3-5h at a certain temperature under a vacuum environment, wherein the temperature range of heat preservation can be set at 120-140 ℃ to obtain BiCl3@ porous carbon composite material. The bismuth chloride @ porous carbon composite chloride ion battery cathode material disclosed by the invention has the cycle performance obviously superior to that of pure BiCl after the chloride ion battery is assembled3Especially after 60 cyclesStill maintain 90mAh g‑1The stable capacity of the device is obviously improved.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a battery anode material technology, and specifically relates to a bismuth chloride @ porous carbon composite chloride ion battery anode material.
Background
With the development of science and technology and the urgent need for renewable energy, electric energy is increasingly gaining attention as a clean energy form that is easy to control and convert, and a secondary battery as an energy storage device plays a crucial role therein. The lithium ion battery which is most widely applied at present is limited by specific energy density, material abundance, cost, safety and the like, and is difficult to meet the increasing requirements of people in the future. Therefore, it is urgent to develop a novel secondary battery having a large storage capacity, excellent performance, good safety, less pollution, and low cost.
Chloride ion batteries, which are based on chloride anion conduction, are a very promising alternative to lithium ion batteries. The positive electrode material (metal chloride, metal oxychloride, chlorine-doped conductive polymer and the like) and the negative electrode material (sodium, magnesium, calcium and the like) used by the chloride ion battery are rich in reserves and low in price. In addition, the battery system of the chloride ion battery has larger free energy change during electrochemical conversion, can generate higher electromotive force, and reports that the theoretical energy density of the metal chloride/metal system can reach 2500Wh L-1Is higher than that of the traditional lithium ion battery (1901Wh L)-1)。
In recent years, although there are many reports on positive electrode materials for chloride ion batteries, research, test, and industrialization of metal chloride positive electrodes have been advanced. In 2013, in a report that the concept of a Chloride ion battery is put forward for the first time in chlorine ion battery, X.Y.ZHao et al, A new member in the rechargeable battery family, use metal Chloride as a positive electrode material, and summarize the main problems faced by the material: the battery of the system hardly has the capacity of repeated charge and discharge due to huge volume change and shuttle effect of being easily dissolved in electrolyte in the charge and discharge process. Thus, in previous studies, metal chlorides, such as CoCl2,VCl3,CuCl2And the like, all of which have only first charge-discharge performance. However, BiCl3As a special case of metal chloride, the metal chloride is insoluble in electrolyte and is the only chloride cathode material with 3-cycle performance reported at present. However, the capacity fade of this material is still quite severe, mainly BiCl3Poor conductivity and charge-discharge of materialLarge volume changes in the electrical process.
Prior art attempts to BiCl3Modified to improve the cycle performance of the application in a chlorine ion battery system, but due to the BiCl3Is very easy to hydrolyze to produce BiOCl even if BiCl3BiOCl impurities also appear after exposure to dry air for several minutes. Therefore, in the conventional improvement process, the whole preparation process is required not to contact with air, and experimental instruments and raw materials and medicines are required to ensure extremely low moisture, otherwise, the purity of a final product is influenced, the batch production difficulty is high, the cost is high, the preparation process consumes a long time, and as long as the preparation process slightly contacts with air, impurities BiOCl are generated, so that the failure risk is obviously increased.
Disclosure of Invention
The invention aims at the BiCl3The defect of poor cycle performance of the material, and provides BiCl with good electrochemical activity3@ porous carbon composite chloride ion battery cathode material.
Another object of the present invention is to provide a method for preparing the above BiCl using porous carbon as a carrier3A method of @ porous carbon composite positive electrode material.
According to a first aspect of the improvement of the present invention, there is provided a BiCl3The preparation method of the @ porous carbon composite chloride ion battery positive electrode material comprises the following steps:
step 1, adding a certain amount of BiCl3Dissolving in hydrochloric acid;
step 2, the BiCl obtained in the step 13Uniformly mixing the solution with a certain amount of porous carbon material, wherein the total pore volume of the porous carbon is more than or equal to the volume of the added hydrochloric acid;
step 3, standing the mixture obtained in the step 2 for at least 12 hours in a vacuum environment;
step 4, carrying out rotary evaporation on the mixture obtained in the step 3 at a certain temperature under a vacuum environment for 3-5h to obtain BiCl3@ porous carbon composite material.
Preferably, the porous carbon material is a carbon material comprising a non-closed pore structure.
Preferably, the porous carbon comprises one of porous carbon foam (MCF), ordered mesoporous carbon CMK-3, Carbon Nanotubes (CNTs).
Wherein the BiCl prepared in step 43In @ porous carbon composite, BiCl3Has a particle size of nanometer order and is dispersed in a porous carbon matrix.
Wherein, in step 2, the amount of porous carbon added is determined by its pore volume and the volume of hydrochloric acid added.
According to a second aspect of the improvement according to the invention, there is also proposed a BiCl prepared according to the aforementioned process3@ porous carbon composite chloride ion battery cathode material.
According to the improved third aspect of the invention, a BiCl is also provided3The @ porous carbon composite anode material for the chloride ion battery comprises nanoscale BiCl3And a porous carbon matrix, said nanoscale BiCl3Uniformly dispersed in a porous carbon matrix, the porous carbon matrix being a carbon material comprising a non-closed pore structure.
Wherein preferably, the porous carbon comprises one of porous carbon foam (MCF), ordered mesoporous carbon CMK-3, Carbon Nanotubes (CNT).
Wherein the final product contains BiCl3The particle size of (a) depends on the pore size of the porous carbon support.
Compared with the prior art, the invention has the remarkable advantages that:
1. in the preparation process of the invention, BiCl is added3The solution is dissolved in hydrochloric acid, so that the solution has low viscosity and can enter the pore canal of the porous carbon in a short time;
2. the vacuum standing process is carried out at room temperature, the evaporation temperature is 140 ℃, the energy consumption and the production cost can be effectively reduced, and the industrialization is easy to realize;
3. the preparation method has simple and easy process, and utilizes the hydrochloric acid to inhibit BiCl3The nature of the hydrolysis, such that BiCl3The hydrochloric acid can contact air under the protection of hydrochloric acid without affecting the purity of the final product, greatly reduces the operation difficulty, improves the preparation success rate, and is suitable for large-scale production. At the same time, knotThe carbon shell of porous carbon, which cooperates as a carrier, not only constitutes a fast continuous electron transport path, but also acts as a good buffer to accommodate the large volume changes of the electrode material during charging and discharging. The complex pore channel structure in the porous carbon can effectively avoid BiCl3While providing a channel for the rapid diffusion of chloride ions;
4. BiCl prepared by the invention3The @ porous carbon composite material has obviously better cycle performance than the traditional pure BiCl after being assembled into the chloride ion battery3The positive electrode material especially still maintains 90mAh g after 60 cycles-1The capacity is remarkably improved when the metal chloride is used as the cathode material of the chloride ion battery.
It should be understood that all combinations of the foregoing concepts and additional concepts described in greater detail below can be considered as part of the inventive subject matter of this disclosure unless such concepts are mutually inconsistent. In addition, all combinations of claimed subject matter are considered a part of the presently disclosed subject matter.
The foregoing and other aspects, embodiments and features of the present teachings can be more fully understood from the following description taken in conjunction with the accompanying drawings. Additional aspects of the present invention, such as features and/or advantages of exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of specific embodiments in accordance with the teachings of the present invention.
Drawings
The drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures may be represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. Embodiments of various aspects of the present invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a BiCl prepared according to the method of the present invention3@ raman spectrogram of porous carbon (example 1) material;
FIG. 2 is BiCl3Scanning electron microscopy of the field emission of the @ porous carbon (example 1) MaterialAnd a corresponding energy spectrum element mapping image;
FIG. 3 is BiCl of example 13@ porous carbon (example 1) material cycling stability curve with discharge capacity (mAh g) on the abscissa-1) The ordinate is the number of cycles (n) and the current density is 10mA g-1。
Detailed Description
In order to better understand the technical content of the present invention, specific embodiments are described below with reference to the accompanying drawings.
In this disclosure, aspects of the present invention are described with reference to the accompanying drawings, in which a number of illustrative embodiments are shown. Embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be appreciated that the various concepts and embodiments described above, as well as those described in greater detail below, may be implemented in any of numerous ways, as the disclosed concepts and embodiments are not limited to any one implementation. In addition, some aspects of the present disclosure may be used alone, or in any suitable combination with other aspects of the present disclosure.
BiCl proposed according to an exemplary embodiment of the present invention3The preparation process of the @ porous carbon composite chloride ion battery cathode material comprises the following steps: adding a certain amount of BiCl3Dissolving in hydrochloric acid; then the obtained BiCl is added3Uniformly mixing the solution with a certain amount of porous carbon material, wherein the total pore volume of the porous carbon is more than or equal to the volume of the added hydrochloric acid; then standing the obtained mixture for at least 12h under a vacuum environment; finally, carrying out rotary evaporation on the obtained mixture for 3-5h at a certain temperature under a vacuum environment, wherein the temperature range of heat preservation can be set at 120-140 ℃ to obtain BiCl3@ porous carbon composite material.
The amount of porous carbon added is determined, among other things, by its pore volume and the volume of hydrochloric acid added.
Thus, BiCl with good electrochemical activity is prepared3@ porous carbon composite chloride ion battery cathode material, such as battery cycle test made by us below, using BiCl prepared by the invention3@ porous carbon composite material as positive electrode of chloride ion battery, and after 60 cycles of cycling, the discharge capacity of the chloride ion battery is 90mAh g-1Compared with the conventional BiCl3The cycle performance of the method is obviously improved.
Preferably, in the preparation process of the present invention, the porous carbon material is a carbon material comprising a non-closed pore structure, such as, inter alia, porous carbon foam (MCF), ordered mesoporous carbon CMK-3, Carbon Nanotubes (CNTs).
The materials used in the various embodiments of the present invention are particularly preferably commercially available solvents, solutions, powders, and other materials. For example, BiCl employed3The raw materials are commercially available or can be prepared by reacting bismuth nitrate with hydrochloric acid according to the method in CN101628735A in the prior art.
The foregoing MCF materials can be prepared according to the method of Jinwood Lee et al, Low-cost and fault synthesis of mesoporous carbon foams. CMK-3 and CNT can be purchased from the market to meet the quality requirement.
Particularly preferably, according to the preparation process requirement of the invention, the mixture of the step 3 is subjected to vacuum standing and can be carried out at room temperature, so that the control and cost of the generation process are greatly reduced, and the energy is saved.
Wherein, the BiCl prepared by combining the field emission scanning electron microscope image shown in FIG. 2 and the corresponding mapping images (Bi, Cl) of the energy spectrum elements3In @ porous carbon composite, BiCl3The particle size of (A) is nano-scale, and the particles are uniformly dispersed in a porous carbon matrix.
The foregoing preparation process and results are more specifically illustrated below with reference to specific preparation examples.
To facilitate the test, we tested MCF material as the porous carbon matrix.
[ example 1 ]
1mL of concentrated HCl (37 wt.%) was placed in a test tube and 1g of BiCl was added3Dissolving, and operating at room temperature. To BiCl3After complete dissolution, 0.65g of MCF was added and stirred well. The mixture was placed in a rotary evaporator and allowed to stand at room temperature under vacuum for 18 h. Then warmThe temperature is raised to 130 ℃, and the BiCl is obtained after rotary evaporation for 5 hours3@ MCF composite.
[ example 2 ]
1mL of concentrated HCl (37 wt.%) was placed in a test tube and 1.2g of BiCl was added3Wait for BiCl3After complete dissolution, 1.5g of CMK-3 was added and stirred well. The mixture was placed in a rotary evaporator and allowed to stand at room temperature under vacuum for 15 h. Then the temperature is raised to 120 ℃, and the BiCl is obtained after rotary evaporation for 5 hours3@ MCF composite.
[ example 3 ]
1mL of concentrated HCl (37 wt.%) was placed in a test tube and 1.5g of BiCl was added3Wait for BiCl3After complete dissolution, 1.5g of CNT was added and stirred well. The mixture was placed in a rotary evaporator and allowed to stand at room temperature under vacuum for 18 h. Then the temperature is raised to 140 ℃, and the BiCl is obtained after rotary evaporation for 3 hours3@ MCF composite material
BiCl prepared in example 1 is shown below in conjunction with FIGS. 1-33The performance test results of the @ porous carbon composite material are further characterized and explained.
As shown in fig. 1, BiCl was measured by raman spectroscopy3Characterization of the @ porous carbon composite material shows that the BiCl prepared3The @ MCF composite has a higher purity.
As shown in FIG. 2, a portion of BiCl was observed by a field emission scanning electron microscope3Attached to the surface of the MCF in a nano sheet shape. As can be seen from the corresponding energy spectrum element mapping image, Bi and Cl elements which are uniformly distributed still exist in the region without the appearance of the nanosheets, which indicates that most of BiCl elements3Into the interior of the porous carbon matrix.
In the preparation process, the invention utilizes hydrochloric acid to inhibit BiCl3The nature of the hydrolysis, such that BiCl3The hydrochloric acid can contact air under the protection of hydrochloric acid without affecting the purity of the final product, greatly reduces the operation difficulty, improves the preparation success rate, and is suitable for large-scale production. Meanwhile, the carbon shell combined with the porous carbon as the carrier not only constitutes a rapid continuous electron transport path but alsoAnd also acts as a good buffer to accommodate the large volume changes of the electrode material during charging and discharging. The complex pore channel structure in the porous carbon can effectively avoid BiCl3While providing a pathway for rapid diffusion of chloride ions.
If BiCl is directly added3It is very difficult to perform the compounding with the porous carbon material. As described in the background, in the experiments we found that BiCl is due to3Is very easy to hydrolyze to produce BiOCl even if BiCl3BiOCl impurities also appear after exposure to dry air for several minutes. Thus, in the examples of the present invention, we have innovatively used the ability of hydrochloric acid to inhibit BiCl3The nature of the hydrolysis, such that BiCl3Can be directly dissolved and placed at normal temperature under the protection of hydrochloric acid, and vacuum rotary evaporation in a low-heating environment is kept, so that the production process with short time and low energy consumption requirements is realized.
We performed on the resulting BiCl3Electrochemical properties of the @ porous carbon composite were further determined according to the following method:
the BiCl prepared in example 1 was taken30.8g of the porous carbon composite, 0.1g of conductive additive carbon black and 0.1g of PVDF are mixed and ground for 0.5h, the powder is uniformly scattered between two stainless steel nets, and the electrode plate is formed by dry pressing (150 bar).
All operations were carried out in a glove box filled with high purity argon, H2O and O2The content is less than 1 ppm.
The metal lithium is taken as a counter electrode and a reference electrode, glass microfilber is taken as a diaphragm to assemble the CR2032 type button cell, and the electrolyte is 0.5M PP14Cl/PP14TFSI solution. Charging and discharging in constant current mode, discharging and recharging the electrode, and the current density is 10mA g-1The cut-off voltage ranges from 1.6 to 4V.
FIG. 3 is a cyclic charge-discharge curve obtained after the constant current mode charge-discharge, from which it can be seen that BiCl is prepared3The initial discharge capacity of the @ porous carbon composite material is 307mAh g-1And a discharge capacity after 60 cycles of 90mAh g-1Compared with the prior art, the method has the advantages that the method is simple in timePure BiCl used in e rechargeable battery family3The cycle performance of a battery system used as a positive electrode material is remarkably improved.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.
Claims (8)
1. BiCl3The preparation method of the @ porous carbon composite chloride ion battery positive electrode material is characterized by comprising the following steps of:
step 1, adding a certain amount of BiCl3Dissolving in hydrochloric acid;
step 2, the BiCl obtained in the step 13Uniformly mixing the solution with a certain amount of porous carbon material, wherein the total pore volume of the porous carbon is more than or equal to the volume of the added hydrochloric acid;
step 3, standing the mixture obtained in the step 2 for at least 12 hours in a vacuum environment;
step 4, carrying out rotary evaporation on the mixture obtained in the step 3 at a certain temperature under a vacuum environment for 3-5h to obtain BiCl3@ porous carbon composite material.
2. The BiCl of claim 13The preparation method of the @ porous carbon composite chloride ion battery cathode material is characterized in that the porous carbon material is a carbon material containing a non-closed pore structure.
3. The BiCl of claim 13The preparation method of the @ porous carbon composite chloride ion battery cathode material is characterized in that the porous carbon comprises one of porous carbon foam (MCF), ordered mesoporous carbon CMK-3 and Carbon Nano Tubes (CNT).
4. The BiCl of claim 13The preparation method of the @ porous carbon composite chloride ion battery positive electrode material is characterized in thatIn step 4, the temperature range of the rotary evaporation process is set to be 120-140 ℃.
5. The BiCl of claim 13The preparation method of the @ porous carbon composite chloride ion battery cathode material is characterized in that the mixture obtained in the step 3 is placed in vacuum and is carried out at room temperature.
6. The BiCl of claim 13The preparation method of the @ porous carbon composite chloride ion battery cathode material is characterized in that the BiCl prepared in the step 4 is3In @ porous carbon composite, BiCl3Has a particle size of nanometer order and is dispersed in a porous carbon matrix.
7. The BiCl of claim 13The preparation method of the @ porous carbon composite chloride ion battery cathode material is characterized in that in the step 2, the amount of the added porous carbon is determined by the pore volume of the porous carbon and the volume of the added hydrochloric acid.
8. BiCl prepared according to the method of any one of claims 1-73@ porous carbon composite chloride ion battery cathode material.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04282571A (en) * | 1991-03-12 | 1992-10-07 | Seiko Epson Corp | Alkali metal-metal chloride battery |
| US20120077079A1 (en) * | 2010-09-28 | 2012-03-29 | Battelle Memorial Institute | Redox Flow Batteries Based on Supporting Solutions Containing Chloride |
| CN104241711A (en) * | 2014-05-16 | 2014-12-24 | 南京工业大学 | Chloride ion battery |
| CN106299288A (en) * | 2016-09-08 | 2017-01-04 | 南京工业大学 | The application in chloride ion cell positive material of the polymer matrix composite of a kind of chlorine doping |
| CN107331838A (en) * | 2017-06-21 | 2017-11-07 | 南京工业大学 | A kind of chlorion cell nano combination electrode material and preparation method thereof |
| CN107665990A (en) * | 2016-07-29 | 2018-02-06 | 横店集团东磁股份有限公司 | A kind of chloride battery positive plate and preparation method thereof |
| CN109411712A (en) * | 2018-09-10 | 2019-03-01 | 天津理工大学 | A kind of novel aluminium chlorine hybrid ionic battery |
| CN111769272A (en) * | 2020-07-28 | 2020-10-13 | 广西师范大学 | Bi @ C hollow nanosphere composite material and preparation method and application thereof |
| DE112019001561T5 (en) * | 2018-03-27 | 2020-12-10 | Honda Motor Co., Ltd. | Positive Electrode Active Material for Fluoride Ion Secondary Batteries, Positive Electrode Using the Active Material, Fluoride Ion Secondary Battery, and Process for Manufacturing the Active Material |
-
2021
- 2021-03-26 CN CN202110328511.6A patent/CN113078312B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04282571A (en) * | 1991-03-12 | 1992-10-07 | Seiko Epson Corp | Alkali metal-metal chloride battery |
| US20120077079A1 (en) * | 2010-09-28 | 2012-03-29 | Battelle Memorial Institute | Redox Flow Batteries Based on Supporting Solutions Containing Chloride |
| CN104241711A (en) * | 2014-05-16 | 2014-12-24 | 南京工业大学 | Chloride ion battery |
| CN107665990A (en) * | 2016-07-29 | 2018-02-06 | 横店集团东磁股份有限公司 | A kind of chloride battery positive plate and preparation method thereof |
| CN106299288A (en) * | 2016-09-08 | 2017-01-04 | 南京工业大学 | The application in chloride ion cell positive material of the polymer matrix composite of a kind of chlorine doping |
| CN107331838A (en) * | 2017-06-21 | 2017-11-07 | 南京工业大学 | A kind of chlorion cell nano combination electrode material and preparation method thereof |
| DE112019001561T5 (en) * | 2018-03-27 | 2020-12-10 | Honda Motor Co., Ltd. | Positive Electrode Active Material for Fluoride Ion Secondary Batteries, Positive Electrode Using the Active Material, Fluoride Ion Secondary Battery, and Process for Manufacturing the Active Material |
| CN109411712A (en) * | 2018-09-10 | 2019-03-01 | 天津理工大学 | A kind of novel aluminium chlorine hybrid ionic battery |
| CN111769272A (en) * | 2020-07-28 | 2020-10-13 | 广西师范大学 | Bi @ C hollow nanosphere composite material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| XIANGYU ZHAO等: "Carbon incorporation effects and reaction mechanism of FeOCl cathode materials for chloride ion batteries", 《SCIENTIFIC REPORTS》 * |
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