CN-122000497-A - High-stability low-temperature proton battery and preparation method thereof

CN122000497ACN 122000497 ACN122000497 ACN 122000497ACN-122000497-A

Abstract

The application discloses a high-stability low-temperature proton battery and a preparation method thereof, which belong to the technical field of proton batteries, wherein a quinone polymer HMND with double active sites is used as a proton storage material, stable deintercalation of protons can be realized in a high-safety proton-containing aqueous solution, the application provides an intramolecular hydrogen bond stabilization strategy to solve the problem of dissolution of organic electrode materials, thereby improving the electrochemical stability of the organic materials, manganese dioxide is used as a positive electrode material, a quinone polymer HMND is used as a negative electrode material, and a sulfuric acid-manganese sulfate solution is used as an electrolyte to prepare the proton battery, the constructed proton battery realizes the specific capacity of 212.5 mAh g ‑1 under the current density of 1A g ‑1 , has the capacity retention rate of 77% after 8A g ‑1 is subjected to 42000 cycles, can well run even in a frozen electrolyte at-60 ℃, and shows the energy storage potential at extreme temperature.

Inventors

BIN DUAN
LIU XIAO
GE RONG
ZHAO HANG
REN XUEQING
LI RUONAN
LU HONGBIN
YANG BEIBEI

Assignees

南通大学

Dates

Publication Date: 20260508
Application Date: 20251224

Claims (10)

1. The preparation method of the high-stability low-temperature proton battery is characterized by comprising the following steps of: firstly, preparing a quinone polymer proton battery anode material: S1, preparing a quinone polymer, namely uniformly mixing a quinone compound and an aromatic amine compound according to a molar ratio of the quinone compound to the aromatic amine compound=5:1, dissolving the mixture in an alcohol reagent, centrifuging the mixture for three times by taking the alcohol reagent as a solvent and then centrifuging the mixture for three times by taking an ester reagent as the solvent after oil bath for 300min at a temperature of 70 ℃ to 100 ℃ and drying the mixture for 12 to 36 hours to obtain the quinone polymer; S2, preparing electrode slurry, namely uniformly mixing 60-80 parts by weight of quinone polymer, 10-30 parts by weight of conductive agent and 10-30 parts by weight of binder to obtain the electrode slurry; s3, preparing an electrode film, namely rolling the electrode slurry into a film with the thickness not exceeding 1 mm on a roll squeezer, drying and cutting into the electrode film with the size of 1 cm multiplied by 1 cm; S4, pressing the electrode film on the current collector to obtain a negative electrode plate, namely the quinone polymer proton battery negative electrode material; secondly, preparing a manganese dioxide proton battery anode material: S21, in an acidic electrolyte containing Mn 2+ , an Ag/AgCl electrode is used as a reference electrode, activated carbon is used as a counter electrode, and commercial graphite felt GF is used as a working electrode to form a three-electrode system, wherein the acidic electrolyte containing Mn 2+ consists of 2M MnSO 4 and 2M H 2 SO 4 ; S22, carrying out constant-current charging on a three-electrode system, washing the obtained MnO 2 @GF with deionized water, and then drying in a vacuum oven at 60 ℃ for 2 hours to obtain a positive electrode sheet, namely a manganese dioxide proton battery positive electrode material; and thirdly, constructing the high-stability low-temperature proton battery by taking the quinone polymer proton battery anode material as an anode, taking the manganese dioxide proton battery anode material as a cathode and taking the mixed solution of the manganese-containing substance and the acid substance as electrolyte.
2. The method for preparing a high-stability low-temperature proton battery according to claim 1, wherein the quinone compound is one or more of 1, 4-benzoquinone, 2, 6-dimethoxy-benzoquinone, anthraquinone-2, 6-disodium disulfonate, naphthoquinone-1, 4-dione, anthraquinone-2-sodium sulfonate, 9, 10-anthraquinone, and the aromatic amine compound is one or more of 1, 5-diaminonaphthalene, 4-aminodiphenylamine, alpha-phenethylamine, N-dimethylaniline, 4-aminobiphenyl, 8-hydroxyquinoline.
3. The preparation method of the high-stability low-temperature proton battery according to claim 1, wherein the alcohol reagent is one or more of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol and tert-butanol, and the ester reagent is one or more of methyl formate, ethyl formate, propyl formate, ethyl acetate, n-propyl acetate, isobutyl acetate, methyl propionate and methyl butyrate.
4. The preparation method of the high-stability low-temperature proton battery as claimed in claim 1, wherein the quinone polymer is prepared by polymerization of 1, 4-benzoquinone and 1, 5-diaminonaphthalene, specifically, 10 mmol of 1, 4-benzoquinone and 2 mmol of 1, 5-diaminonaphthalene are taken, ground in a mortar for 30 min, mixed uniformly, dissolved in 50 mL absolute ethyl alcohol, placed in a three-neck flask, cooled to room temperature after oil bath 300 min at a temperature of 70 ℃ and a rotating speed of 600 r/min, centrifuged for three times by using absolute ethyl alcohol as a solvent, centrifuged for three times by using ethyl acetate, and placed in a vacuum drying box for drying at 70 ℃ for 12h after centrifugation, thus obtaining the quinone polymer, namely HMND material.
5. The method of claim 1 wherein the conductive agent is one or more of Ketjen black, activated carbon, mesoporous carbon, graphene, carbon nanotubes, carbon fibers, acetylene black, and carbon black.
6. The method for preparing a high-stability low-temperature proton battery according to claim 1, wherein the binder is one or more of polytetrafluoroethylene, polyvinylidene fluoride, polyolefin, polyvinyl alcohol and styrene-butadiene rubber.
7. The method of claim 1 wherein the current collector is a solid grid with high electron conductivity, and the solid grid is one or more of conductive graphite mesh, titanium mesh, nickel mesh, molybdenum mesh, copper mesh, aluminum mesh, and stainless steel mesh.
8. The method for preparing the high-stability low-temperature proton battery as claimed in claim 1, wherein the manganese-containing substance in the third step is one or more of manganese sulfate, manganese chloride, manganese nitrate, manganese carbonate, potassium permanganate and manganese acetate, and the acid-containing substance is one or more of sulfuric acid, nitric acid, hydrochloric acid, perchloric acid and glacial acetic acid.
9. The method for preparing a high-stability low-temperature proton battery as claimed in claim 1, wherein the concentration of Mn 2+ and H + in the mixed solution of the manganese-containing substance and the acid-containing substance is 0.5-2 mol/L.
10. A high stability low temperature proton battery prepared by the method of any one of claims 1 to 9, wherein the high stability low temperature proton battery can be operated at a temperature of-60 ℃.

Description

High-stability low-temperature proton battery and preparation method thereof Technical Field The invention belongs to the technical field of proton batteries, and particularly relates to a high-stability low-temperature proton battery and a preparation method thereof. Background Development of efficient, safe and sustainable novel electrochemical energy storage technologies has become the leading edge and hotspot of scientific research. With the rapid development of renewable energy sources (e.g., solar energy, wind energy), the need for large-scale energy storage systems is becoming increasingly stringent. Among the many energy storage technologies, aqueous proton batteries have received widespread attention in recent years as an emerging energy storage system. Protons have incomparable advantages as charge carriers, minimum ionic radius, lightest atomic mass, and unique Grotthuss conduction mechanisms. This "jump" proton transport mode allows the proton cell to have ultra-fast ion transport kinetics and potentially high power densities. The migration of protons in aqueous solution is more efficient than conventional metal ions (such as Li +、Na+、Zn2+), which provides new possibilities for developing high rate performance energy storage devices. However, proton batteries still face significant challenges, and the problem of dissolution of small molecule organic materials in the electrolyte severely affects the cycling stability of the battery. Taking p-Benzoquinone (BQ) as an example, its high solubility in acidic electrolytes causes continuous loss of active substances and rapid capacity fade. Secondly, most organic materials have poor electron conductivity, limiting the exertion of their rate capability. In addition, the organic material has large volume change in the charge and discharge process, and is easy to cause structural damage and performance degradation. These problems severely limit the practical application of organic electrode materials in proton batteries. In view of these perspectives, the search for the design and synthesis of novel organic electrode materials is critical to the construction of high performance proton batteries. Aiming at the key challenges faced by the current organic electrode materials in the application of water-based proton batteries, including the problems of poor circulation stability, easy dissolution of active substances, insufficient electronic conductivity and the like, the application creatively provides a strategy for systematically improving the material performance by constructing an intramolecular hydrogen bond network. The core of the design thought is to optimize the structural characteristics and electrochemical behaviors of the material from the molecular level by utilizing the special action mechanism of intramolecular hydrogen bonds. Specifically, a class of quinone polymer materials containing intramolecular hydrogen bonds is designed and successfully synthesized. The formation of intramolecular hydrogen bonds significantly enhances the rigid structure of the molecule and effectively inhibits the dissolution tendency of the material in the electrolyte. More importantly, these hydrogen bond networks build stable spatial configurations, providing an ordered channel system for proton transport. From the molecular structure point of view, the hydrogen bonding action enables the polymer framework to form a more regular plane structure, which not only improves the crystallinity of the material, but also promotes the delocalization effect of pi electrons. Through the design of the intramolecular hydrogen bond strategy, not only the key problem faced by the organic electrode material in proton battery application is successfully solved, but also a new idea is provided for developing the high-performance organic electrode material. The strategy starts from the design of a molecular structure, and through accurately regulating and controlling a hydrogen bond network, the system improvement of the comprehensive performance of the material is realized, and an important material foundation is laid for the development of proton battery technology. Disclosure of Invention The technical problem to be solved is that a quinone polymer stabilization strategy containing intramolecular hydrogen bonds is provided for solving the technical problem of dissolution of the traditional organic electrode material, so that the electrochemical stability of the organic material is remarkably improved, meanwhile, the pi conjugation effect of the quinone polymer is improved, so that the charge transfer dynamics is improved, the electronic conductivity of the organic material is improved, the water-based proton battery has the characteristics of intrinsic safety, high cost efficiency, high ionic conductivity, environmental friendliness and the like, has important significance in the fields of large-scale energy storage and small wearable equipment, and protons are ideal charge carrier