CN-117080583-B - Ca-I2Preparation method of double-ion battery

Abstract

The invention relates to the technical field of calcium ion batteries, in particular to a preparation method of a Ca-I 2 double-ion battery, which comprises the following steps of (1) placing a 5M CaCl 2 aqueous solution as an electrolyte in an electrolytic cell, (2) placing elemental iodine and activated carbon fiber cloth in a sealed glass container together for iodine fixation, and taking the carbon fiber cloth after iodine fixation as a positive electrode material, (3) drying carbon fiber paper coated with slurry to obtain an electrode plate, carrying out electrochemical cyclic voltammetry activation on the electrode plate after full drying, and taking the electrode plate after activation as a negative electrode material, (4) placing the positive electrode material and the negative electrode material in the electrolyte together, and obtaining the Ca-I 2 double-ion battery through matching.

Inventors

• DENG TING
• ZHENG YING
• ZHENG WEITAO

Assignees

• 吉林大学

Dates

Publication Date

20260512

Application Date

20230901

Claims (6)

1. 1. The preparation method of the Ca-I 2 double-ion battery is characterized by comprising the following steps of: (1) Placing a 5M CaCl 2 aqueous solution as an electrolyte of the Ca-I 2 double-ion battery in an electrolytic cell; (2) Putting the elemental iodine and the activated carbon fiber cloth into a sealed glass container together for iodine fixation, wherein the carbon fiber cloth after iodine fixation is used as a positive electrode material; (3) The method comprises the steps of drying carbon fiber paper coated with slurry to obtain an electrode slice, and performing electrochemical cyclic voltammetry activation on the electrode slice after full drying, wherein the electrode slice after activation is used as a negative electrode material; (4) The positive electrode material obtained in the step (2) and the negative electrode material obtained in the step (3) are placed in the electrolyte in the step (1) together, and the Ca-I 2 double-ion battery is obtained through matching; In the step (3), the slurry is prepared from C 24 H 10 N 2 O 4 , super P and Nafion film solution according to the mass ratio of 7:1.5:1.5, and ethanol is used as a solvent; In the step (3), the activation method of the electrochemical cyclic voltammetry specifically comprises the following steps: the platinum sheet and the saturated calomel electrode are used as a counter electrode and a reference electrode, the electrode sheet is used as a working electrode, 0.5M CaCl 2 is used as electrolyte, the scanning speed is 3 mV s -1 , and the scanning potential range is-1-0V.
2. 2. The method for preparing a Ca-I 2 bi-ionic cell according to claim 1, wherein in step (2), before iodine fixing, the carbon fiber cloth is first air annealed in a muffle furnace to construct a multi-stage pore structure on the surface, wherein the temperature in the muffle furnace is 450 ℃, and the annealing time is 2 hours.
3. 3. The method for producing a Ca-I 2 bi-ionic cell according to claim 2, wherein in step (2), the elemental iodine is first sufficiently ground into a powder before solidification of iodine is performed.
4. 4. A method for producing a Ca-I 2 bi-ionic cell according to any one of claims 1 to 3, wherein in step (2), elemental iodine and activated carbon fiber cloth are put together in a sealed glass container, the sealed glass container is put in a blast drying oven, reacted at 120 ℃ for 3 hours, cooled to 80 ℃ with the oven, kept for one hour, cooled to room temperature, and the elemental iodine is completely volatilized and fixed on the surface of the carbon fiber.
5. 5. The method for preparing a Ca-I 2 bi-ionic cell according to claim 1, wherein in step (3), the carbon fiber paper is cut into a rectangle of 1 x 1.5 cm 2 , and is ultrasonically cleaned with acetone, ethanol and deionized water for 20 minutes, respectively, and the cleaned carbon fiber paper is placed into an oven at 60 ℃ and dried sufficiently.
6. 6. The method for producing a Ca-I 2 bi-ionic cell according to claim 1, wherein in step (3), the temperature at which the electrode sheet is dried is 60 ℃.

Description

Preparation method of Ca-I 2 double-ion battery Technical Field The invention relates to the technical field of calcium ion batteries, in particular to a preparation method of a Ca-I 2 double-ion battery. Background As a polyvalent metal ion battery, a calcium ion battery has been widely studied for its advantages such as higher charge transfer number, higher theoretical specific capacity (1337 mAh g -1) due to the absence of dendrites. The working principle of the calcium ion battery is similar to that of a lithium ion battery, and in the charging process, calcium ions migrate from the positive electrode to the negative electrode through electrolyte to react with the positive electrode, and in the discharging process, calcium ions migrate from the negative electrode to the positive electrode to react with the negative electrode. The selection of positive and negative electrode materials and electrolyte directly affects the performance of the whole calcium ion battery, and the negative electrode materials are mainly classified into three main categories according to the difference of energy storage mechanisms of the materials, namely Ca metal anodes, alloy compound anodes and intercalation anode materials. The Ca metal is directly used as an anode to generate deposition/peeling reaction in the charge and discharge process, ca reserves are rich and can be directly used as the anode, but many researches find that the surface of the Ca anode can irreversibly form a passivation layer to block a diffusion channel of Ca ions in the reaction process, so that the coulombic efficiency of a battery is lower due to the inhibition of the reversible deposition/peeling reaction of the Ca ions, only few ether type organic crystals can inhibit the formation of a passivation film at present so as to support the reversible deposition/peeling reaction of metal Ca, the alloy compound anode generally has higher specific discharge capacity, and calcium and silicon form an intermetallic compound Ca x Si phase at the voltage of about 0.37V, and for an intercalation anode material, the Ca ions are often intercalated into an interlayer to form an intercalation compound in the discharge process. For the positive electrode material of the calcium ion battery, intercalation and deintercalation reaction often occurs, and the material comprises layered oxide (such as Ca 0.28V2O5⋅H2 O, calcium ions are deintercalated from Ca 0.28V2O5⋅H2 O in the charging process and migrate to the negative electrode through electrolyte), prussian blue analogues (such as K 2BaFe(CN)6), Polyanionic compounds (e.g., na 2FePO4 F in a layered structure), transition metal oxides (e.g., caMn 2O4), and organic electrode materials (e.g., C 24H8O6). The performance of the calcium ion battery is directly determined by matching the positive electrode material and the negative electrode material. For example, the intermediate-phase carbon microsphere with an intercalation and deintercalation reaction mechanism is selected as a cathode material, ca 0.28V2O5⋅H2 O is selected as an anode material, calcium ions are deintercalated from Ca 0.28V2O5⋅H2 O through electrolyte to be intercalated into the intermediate-phase carbon microsphere in the whole battery charging process, and calcium ions are deintercalated from the intermediate-phase carbon microsphere through electrolyte to be intercalated into Ca 0.28V2O5⋅H2 O in the discharging process. At present, the configuration of the calcium ion battery mainly comprises that calcium ions shuttle back and forth between anode and cathode materials to realize conversion from chemical energy to electric energy, but because the radius of the calcium ions is larger, the calcium ions have slower dynamic process in the whole transmission process, thereby influencing the multiplying power performance and the power performance of the battery. Disclosure of Invention The invention aims to provide a preparation method of a Ca-I 2 double-ion battery, which aims to solve the problems in the background technology. In order to achieve the above purpose, the present invention provides the following technical solutions: The preparation method of the Ca-I 2 double-ion battery specifically comprises the following steps: (1) Placing a 5M CaCl 2 aqueous solution as an electrolyte of the Ca-I 2 double-ion battery in an electrolytic cell; (2) Putting the elemental iodine and the activated carbon fiber cloth into a sealed glass container together for iodine fixation, wherein the carbon fiber cloth after iodine fixation is used as a positive electrode material; (3) The method comprises the steps of drying carbon fiber paper coated with slurry to obtain an electrode slice, and performing electrochemical cyclic voltammetry activation on the electrode slice after full drying, wherein the electrode slice after activation is used as a negative electrode material; (4) And (3) placing the positive electrode material obtained in the step (2) and the n