An all-solid-state conductive organic polymer proton battery and a preparation method thereof

Abstract

The application discloses a kind of all-solid-state conductive organic polymer proton battery and preparation method thereof, the battery includes positive, negative and all-solid-state proton membrane;The positive and negative electrode both include current collector, and electrode active material layer is supported on the current collector;The electrode active material layer includes the mass ratio of (6.75~7.5):(0.75~1.5):(1~2.5) conductive organic polymer, dispersing agent and binder;The conductive organic polymer is one or more than one in nanocomposite material formed by polypyrrole, polythiophene, polyaniline, polydioxothiophene, poly-p-phenylenevinylene and carbon nanomaterial;The all-solid-state proton membrane is the polymer / inorganic hybrid membrane formed by polymer, functional inorganic nanosol and acid under room temperature condition.The proton battery of the application has the advantages of simple preparation process, safe and reliable use, excellent cycle stability and the like, and has great application potential in the field of energy storage and power battery.

Description

Technical Field

[0001] This invention belongs to the field of solid-state proton battery technology, specifically relating to an all-solid-state conductive organic polymer proton battery and its preparation method. Background Technology

[0002] Developing various energy storage technologies to support the generation and utilization of renewable energy has been considered a possible path to achieving carbon neutrality. With the increasing demand for energy storage, solid-state batteries have become a hot topic in energy storage technology development due to their high safety, high energy density, and environmental friendliness. To date, technologies based on metal ions (Li₂) have been widely adopted. + Na + Zn 2+ Mg 2+ And Al 3+ Batteries, using protons as charge carriers, have been widely studied and applied. However, their diffusion kinetics are limited by large ionic radii. + It has the smallest radius (approximately 0.89 fm) and the lightest weight (1.0 g·mol⁻¹). -1 Due to its rapid reaction kinetics and long-term cycle stability, proton charge carrier (PCC) has become a unique ion charge carrier in batteries. Furthermore, hydrogen is ubiquitous on Earth, thus proton charge carrier-based batteries offer advantages in terms of low cost and resource sustainability.

[0003] Aqueous proton batteries have attracted considerable research interest. For example, CN116470109A discloses an aqueous organic-hydrogen proton battery. However, the all-organic anode material in this battery suffers from dissolution issues in the electrolyte, and its relatively low reduction potential compared to hydrogen evolution results in poor cycle stability. CN112531162A discloses an aqueous proton battery electrode based on a nitrogen-hexaconjugated porous polymer and its preparation method. However, the electrode material in this battery undergoes structural expansion and contraction during proton or hydrated proton insertion and extraction. Furthermore, the proposed acidic electrolyte presents significant challenges regarding its corrosiveness to the battery components, electrode-electrolyte interface compatibility, and low-temperature performance. EP3000142B1 describes a proton battery constructed using graphene derivatives as electrode materials, but this suffers from high material costs and stringent humidity requirements. Therefore, currently, technologies for industrializing aqueous proton batteries are still limited, and the development of new solid-state proton batteries and related electrode materials is urgently needed. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides an all-solid-state conductive organic polymer proton battery and its fabrication method. Utilizing the excellent reversible redox activity and acid doping / dedoping characteristics of conductive organic polymers as symmetrical electrode materials, and employing a polymer / inorganic hybrid membrane as the proton membrane, an all-solid-state proton battery is constructed. This all-solid-state proton battery possesses advantages such as simple fabrication process, safe and reliable use, excellent cycle stability, wide operating temperature range, low raw material cost, and easy packaging, demonstrating significant application potential in the fields of energy storage and power batteries.

[0005] This invention is achieved through the following technical solution:

[0006] A solid-state conductive organic polymer proton battery includes a positive electrode, a negative electrode, and a solid-state proton membrane. Both the positive and negative electrodes include a current collector and an electrode active material layer loaded on the current collector. The electrode active material layer comprises a conductive organic polymer, a dispersant, and a binder in a mass ratio of (6.75–7.5):(0.75–1.5):(1–2.5). The conductive organic polymer is one or more of a nanocomposite material formed from polypyrrole, polythiophene, polyaniline, polydioxythiophene, poly(p-phenylenevinylene), and carbon nanomaterials. The solid-state proton membrane is a polymer / inorganic hybrid membrane formed by a polymer, functionalized inorganic nanosol, and an acid at room temperature.

[0007] Preferably, the dispersant is one or more of sodium oleate, polycarboxylate, sulfonate, polyethylene glycol, and polymeric superdispersant.

[0008] Preferably, the adhesive is one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethyl cellulose, sodium alginate, styrene-butadiene rubber, perfluorosulfonic acid, polyurethane, polyacrylate, and polyvinyl alcohol.

[0009] Preferably, in the all-solid proton membrane, the solid mass ratio of the polymer to the functionalized inorganic nanosol is 1:1 to 1:3.

[0010] Preferably, the polymer is one or more of polyacrylamide, polyacrylic acid, polyvinyl alcohol, chitosan, cellulose, and polyurethane.

[0011] Preferably, the functionalized inorganic nanosol is one or more of nano-titanium dioxide, nano-silica, and nano-cerium dioxide.

[0012] Preferably, the acid is one or more of inorganic acids and organic acids; the inorganic acid is sulfuric acid or phosphoric acid; and the organic acid is sulfosuccinic acid or dodecylbenzenesulfonic acid.

[0013] Preferably, the electrode material of the current collector is one or more of carbon paper, carbon cloth, conductive cloth, graphene felt, and stainless steel mesh.

[0014] The above-mentioned method for preparing an all-solid-state conductive organic polymer proton battery includes the following steps:

[0015] Step 1) Mix the conductive organic polymer, dispersant, and binder evenly according to the ratio to prepare an electrode active material coating; then coat the prepared electrode active material coating evenly on the current collector and dry it in an oven at 80°C for 4 hours to obtain the electrode.

[0016] Step 2) Mix the polymer solution or latex, functionalized inorganic nanosol and acid at room temperature in a certain proportion to obtain a proton exchange membrane solution; then cast the obtained proton exchange membrane solution into a mold and dry it at room temperature to constant weight to obtain a polymer / inorganic hybrid membrane.

[0017] Step 3) Use the electrodes obtained in Step 1) as positive and negative electrodes respectively, and separate them with the polymer / inorganic hybrid membrane obtained in Step 2) to assemble them into a battery.

[0018] The beneficial effects of this invention are as follows:

[0019] (1) The all-solid-state conductive organic polymer proton battery of the present invention, during charging, protons of conductive organic polymer (positive electrode) are released and diffuse to negative electrode through solid proton membrane. During discharging, protons diffuse from negative electrode to positive electrode and are embedded in positive electrode to complete charge-discharge cycle, and the cycle is stable.

[0020] (2) The all-solid-state conductive organic polymer proton battery of the present invention loads conductive polymer electrode material on carbon current collector. The current collector and the electrode material form π-π interaction, which can significantly reduce charge transfer resistance and make the battery rate performance excellent.

[0021] (3) The all-solid-state conductive organic polymer proton battery of the present invention effectively solves the problems of electrolyte corrosion, leakage and narrow temperature range in aqueous proton batteries by using an all-solid-state proton membrane instead of a separator and electrolyte, which greatly improves the safety and resource sustainability of use.

[0022] (4) The all-solid-state conductive organic polymer proton battery of the present invention achieves the theoretical capacity of organic polymers, demonstrating the nanocomposite effect of carbon nanomaterials and organic polymers in conductive organic polymers. Moreover, the battery has low manufacturing cost, simple preparation process, and is easy to mass-produce, and can be widely used in the fields of large-scale energy storage and power batteries. Attached Figure Description

[0023] Figure 1 The mechanical property test results are for the polymer / inorganic hybrid membranes prepared in Examples 1, 3, and 4.

[0024] Figure 2 Electrochemical impedance spectroscopy diagrams of the all-solid-state conductive polyaniline symmetric proton batteries prepared in Examples 1 and 10;

[0025] Figure 3 This is a schematic diagram of the electrode reaction and proton transport of the all-solid-state conductive polyaniline symmetric proton battery prepared in Example 1.

[0026] Figure 4 The all-solid-state conductive polyaniline symmetric proton battery prepared in Example 1 operates at 5–50 mV·s. -1 Cyclic voltammetry curve at scan rate;

[0027] Figure 5 The all-solid-state conductive polyaniline symmetric proton battery prepared in Example 1 was tested at 0.1 A·g -1 up to 1A·g -1 Electrochemical performance test results within the current density range: A is the result of rate charge-discharge test, and B is the result of rate cycle performance test.

[0028] Figure 6 The all-solid-state conductive polyaniline symmetric proton battery prepared in Example 1 was tested at 0.1 A·g -1 Figure showing the results of the cycling performance test at current density. Detailed Implementation

[0029] This invention provides an all-solid-state conductive organic polymer proton battery, comprising a positive electrode, a negative electrode, and an all-solid-state proton membrane; wherein both the positive and negative electrodes include a current collector and an electrode active material layer loaded on the current collector, the electrode active material layer comprising a conductive organic polymer, a dispersant, and a binder.

[0030] According to the embodiments disclosed in this invention, the conductive organic polymer includes one or more of the following: polypyrrole, polythiophene, polyaniline, polydioxothiophene, poly(p-phenylenevinylene) and nanocomposite materials (carbon nanotubes or graphene) (any conductive polymer with redox activity is acceptable). The all-solid-state proton battery system provided in the embodiments of this invention is also applicable to other conductive organic polymers with proton redox activity.

[0031] According to the embodiments disclosed in this invention, the electrode active material layer further includes a binder and a dispersant;

[0032] The binder includes one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethyl cellulose, sodium alginate, styrene-butadiene rubber, perfluorosulfonic acid, polyurethane, polyacrylate, and polyvinyl alcohol. These binders can all form films at room temperature and can be used as binders for electrode active particles.

[0033] The dispersant includes one or more of sodium oleate, polycarboxylate, sulfonate, polyethylene glycol, and high molecular weight superdispersant (any dispersant that has a dispersing function for the above-mentioned conductive organic polymers is acceptable).

[0034] In the embodiments disclosed in this invention, a conductive organic polymer, a dispersant, and a binder are mixed in a certain proportion to form an electrode active material layer. The mass ratio of the conductive organic polymer, the dispersant, and the binder is (6.75-7.5):(0.75-1.5):(1-2.5). Different binders and dispersants will result in different amounts, and therefore the proportion will vary. However, as long as the proportion is within this range, the electrode active material layer obtained will have good electrochemical performance.

[0035] According to the embodiments disclosed in this invention, the electrode material for the current collector includes one or more of the following: carbon paper, carbon cloth, conductive cloth, graphene felt, and stainless steel mesh (any acid-resistant and conductive material is acceptable).

[0036] According to the embodiments disclosed in this invention, the all-solid proton exchange membrane is a polymer / inorganic hybrid membrane formed by mixing one or more polymers such as polyacrylamide, polyacrylic acid, polyvinyl alcohol, chitosan, cellulose, and polyurethane (these polymers can be dissolved in water or prepared into latex), and one or more functionalized inorganic nanosols such as nano-titanium dioxide, nano-silica, and nano-cerium dioxide (stable inorganic nanocolloids are acceptable), and one or more acids such as inorganic acids (sulfuric acid, phosphoric acid) and organic acids (sulfosuccinic acid, dodecylbenzenesulfonic acid) (acids that can form hydrogen bonds with organic polymers and inorganic nanosols) at room temperature, wherein the solid mass ratio of the polymer to the functionalized inorganic nanosol is 1:1 to 1:3.

[0037] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0038] Example 1

[0039] A method for preparing an all-solid-state conductive organic polymer proton battery, the specific steps of which are as follows:

[0040] (1) Electrode preparation

[0041] Conductive polyaniline (a nanocomposite material with a graphene to polyaniline mass ratio of 1:9) was prepared using a nano-sand mill and a polymeric superdispersant to prepare an aqueous nanoslurry with a solid content of 15 wt%. 10 g of the above nanoslurry was then mixed with 1.4 g of 35 wt% polyurethane latex to prepare a conductive polyaniline electrode coating.

[0042] The above-mentioned conductive polyaniline electrode coating was uniformly coated onto the conductive cloth current collector using a scraper, and dried in an oven at 80°C for 4 hours to obtain the conductive polyaniline electrode. The active material loading was 1 mg / cm³. 2 .

[0043] (2) Preparation of polymer / inorganic hybrid membranes

[0044] 10 g of 10 wt% polyvinyl alcohol aqueous solution, 10 g of 30 wt% nano-silica sol modified with ethyl trimethylsilyl ether and γ-glycidyl etheroxypropyltrimethoxysilane (functionalized inorganic nano-sol particles with methyl and epoxy functional groups on the surface) and 1.85 g of phosphoric acid were added to a 100 mL beaker. After stirring evenly, a proton exchange membrane solution (phosphoric acid concentration of 1 mol / L) was obtained.

[0045] The above proton exchange membrane solution was cast onto a polytetrafluoroethylene mold and dried at room temperature to constant weight to obtain a polymer / inorganic hybrid membrane, i.e., an all-solid proton exchange membrane.

[0046] (3) Battery assembly

[0047] The above-mentioned conductive polyaniline electrode sheet was cut into 1.13cm pieces. 2 The discs are used as positive and negative electrodes, separated by a polymer / inorganic hybrid membrane, and assembled into a coin cell.

[0048] Example 2

[0049] A method for preparing an all-solid-state conductive organic polymer proton battery, the specific steps of which are as follows:

[0050] (1) Electrode preparation

[0051] Conductive polyaniline (a nanocomposite material with a graphene to polyaniline mass ratio of 1:9) was prepared using a nano-sand mill and a polymeric superdispersant to prepare an aqueous nanoslurry with a solid content of 15 wt%. 10 g of the above nanoslurry was then mixed with 1.5 g of a 35 wt% polyvinyl alcohol aqueous solution to prepare a conductive polyaniline electrode coating.

[0052] The above-mentioned conductive polyaniline electrode coating was uniformly coated onto a graphene felt current collector using a doctor blade and dried in an oven at 80°C for 4 hours to obtain a conductive polyaniline electrode. The active material loading was 1 mg / cm³. 2 .

[0053] (2) Preparation of polymer / inorganic hybrid membranes

[0054] 10 g of 10 wt% polyvinyl alcohol aqueous solution, 10 g of 30 wt% nano-silica sol modified with ethyl trimethylsilyl ether and γ-glycidyl etheroxypropyltrimethoxysilane (functionalized inorganic nano-sol particles with methyl and epoxy functional groups on the surface) and 1.85 g of phosphoric acid were added to a 100 mL beaker. After stirring evenly, a proton exchange membrane solution (phosphoric acid concentration of 1 mol / L) was obtained.

[0055] The above proton exchange membrane solution was cast onto a polytetrafluoroethylene mold and dried at room temperature to constant weight to obtain a polymer / inorganic hybrid membrane, i.e., an all-solid proton exchange membrane.

[0056] (3) Battery assembly

[0057] The above-mentioned conductive polyaniline electrode sheet was cut into 1.13cm pieces. 2 The discs are used as positive and negative electrodes, separated by a polymer / inorganic hybrid membrane, and assembled into a coin cell.

[0058] Example 3

[0059] A method for preparing an all-solid-state conductive organic polymer proton battery, the specific preparation steps are the same as in Example 1, except that the concentration of phosphoric acid in the proton membrane solution is 1.3 mol / L.

[0060] Example 4

[0061] A method for preparing an all-solid-state conductive organic polymer proton battery, the specific preparation steps are the same as in Example 1, except that the phosphoric acid concentration in the proton membrane solution is 0.7 mol / L.

[0062] Example 5

[0063] A method for preparing an all-solid-state conductive organic polymer proton battery, the specific preparation steps are the same as in Example 2, except that: the electrode material of the current collector is carbon paper, and the phosphoric acid concentration in the proton membrane solution is 1.3 mol / L.

[0064] Example 6

[0065] A method for preparing an all-solid-state conductive organic polymer proton battery, the specific preparation steps are the same as in Example 1, the difference being that the functionalized inorganic nanosol particles have methyl functional groups on their surface.

[0066] Example 7

[0067] A method for preparing an all-solid-state conductive organic polymer proton battery, the specific preparation steps are the same as in Example 1, the difference being that the functionalized inorganic nanosol particles have epoxy functional groups on their surface.

[0068] Example 8

[0069] A method for preparing an all-solid-state conductive organic polymer proton battery, with the same steps as in Example 2, except that the electrode material of the current collector is conductive cloth, and the polymer in the proton membrane is replaced by polyurethane instead of polyvinyl alcohol.

[0070] Example 9

[0071] A method for preparing an all-solid-state conductive organic polymer proton battery, with the same steps as in Example 2, except that the electrode material of the current collector is conductive cloth, and the polymer in the proton membrane is replaced by polyacrylic acid instead of polyvinyl alcohol.

[0072] Example 10

[0073] A method for preparing an all-solid-state conductive organic polymer proton battery, the specific preparation steps are the same as in Example 2, except that the electrode material of the current collector is conductive cloth.

[0074] Test Example 1

[0075] The electrochemical performance test results of the all-solid-state conductive organic polymer proton batteries prepared in Examples 1-9 are shown in Table 1 below:

[0076] Table 1 Electrochemical performance tests of Examples 1-7

[0077]

[0078]

[0079] As shown in Table 1, compared with Examples 1 and 2, the current collector in Example 2 uses graphene felt, even at 5 A·g -1 It can still perform at a current density of 258 mAh·g -1 The specific capacity is as high as 88%, and the capacity retention rate is as high as 91% after 5000 charge-discharge cycles. This is because graphene felt has better conductivity than conductive cloth, which can effectively reduce charge transfer resistance and internal resistance during charge-discharge cycles, thereby improving charge-discharge efficiency. Similarly, comparing Examples 3 and 5, the current collector in Example 5 uses carbon paper. Due to the superior conductivity of carbon paper, the proton battery in Example 5 exhibits superior electrochemical performance.

[0080] Compared to Example 1, the molar concentration of phosphoric acid in the proton exchange membrane solution was changed in Examples 3 and 4 to 1.3 M and 0.7 M, respectively. The electrochemical test results of Example 4 were similar to those of Example 1, but Example 3 exhibited poorer electrochemical performance, with the capacity retention dropping to 71% after only 190 cycles. This is closely related to the mechanical properties of the proton exchange membrane. Figure 1As shown, the molar concentration of phosphoric acid has a significant impact on the mechanical properties of the proton exchange membrane. When the molar concentration of phosphoric acid is 1.3 M, the proton exchange membrane exhibits the lowest tensile strength, which makes it difficult to maintain the mechanical stability of the proton transport channel during battery cycling.

[0081] Compared with Example 1, the proton membranes of Examples 6 and 7 use methylated and epoxy-based nano-silica, respectively. Example 6 exhibits the worst electrochemical performance, while Example 7 shows the largest initial specific capacity. This is because the epoxy groups on the surface of the nano-silica particles participate in the formation of polymer inorganic hybrid structures. The "O" groups are conducive to the formation of proton channels, thereby improving the specific capacity.

[0082] Compared to Example 2, Examples 8 and 9 changed the type of polymer in the proton exchange membrane, using polyurethane and polyacrylic acid respectively. The solid proton exchange membranes prepared could still transport protons, but compared to the all-solid-state proton exchange membranes constructed from polyvinyl alcohol, polyurethane, and polyacrylic acid showed a certain decrease in specific capacity, but their rate performance and cycle stability were still excellent. This is because the network pore sizes formed between different polymers and inorganic nanoparticles are not entirely the same, and the different composition and structure of the proton exchange membranes result in differences in the proton transport efficiency of the proton channels.

[0083] Comparing Examples 1 and 10, the effects of changing the type and amount of binder in the conductive polymer coating of the electrode on the electrochemical impedance spectroscopy are as follows: Figure 2 As shown, by Figure 2 It can be seen that the charge transfer resistance of Example 1 is significantly increased compared to Example 10. This is because polyvinyl alcohol solution is more effective at bonding conductive polymer active materials than polyurethane latex, and the increased mass fraction of non-conductive binder leads to an increase in charge transfer resistance. Example 10 uses polyvinyl alcohol as a binder, and the all-solid proton membrane also contains polyvinyl alcohol components, resulting in a more compatible solid-solid interface compared to Example 1. Therefore, Example 10 has a lower solution resistance. The barrier layer of Example 10 is larger than that of Example 1, indicating that the proton transport channels inside the electrode material are less unobstructed than those in Example 1. This is because stronger hydrogen bonds are formed inside the active electrode material with a larger mass fraction, and protons form proton transport channels through "O" and "N" atoms.

[0084] Test Example 2

[0085] The electrochemical performance of the all-solid-state conductive organic polymer proton battery prepared in Example 1 was tested separately, and the test results are as follows: Figure 4-6 As shown.

[0086] like Figure 3The diagram illustrates the electrode reactions and proton transport in an all-solid-state conductive polyaniline symmetric proton cell, with the all-solid-state proton membrane separating the positive and negative electrodes. During charging / discharging, the redox reactions in the conductive polyaniline are accompanied by the extraction and insertion of protons through the proton transport channels in the proton membrane.

[0087] like Figure 4 The image shows an all-solid-state conductive polyaniline symmetric proton cell in the range of 5–50 mV·s. -1 Cyclic voltammetry curves over the scan rate range show a pair of redox peaks at 0.5 / 0.2V above 0V, indicating that the all-solid-state proton battery has rapid kinetic characteristics and excellent reversibility.

[0088] At 25°C, the performance of an all-solid-state conductive polyaniline symmetric proton cell at 0.1 A·g was tested. -1 up to 1A·g -1 Electrochemical performance within the current density range, performance test results are as follows: Figure 5 As shown.

[0089] The results of the rate charge / discharge test are as follows: Figure 5 As shown in Figure A, the all-solid-state proton cell exhibits a distinct voltage plateau at different current densities, even at 1 A·g -1 Even now, it still boasts a 231mAh·g capacity. -1 High specific capacity. Furthermore, in charge-discharge rate cycling tests, such as... Figure 5 As shown in Figure B, when the current density increases from 1 A·g -1 Restored to 0.1 A·g -1 When the capacity is fully restored to its initial capacity, the all-solid-state proton battery demonstrates excellent rate performance. At different current densities, the coulombic efficiency of the all-solid-state conductive polyaniline symmetric proton battery is close to 100%, exhibiting excellent reversibility. This demonstrates that the all-solid-state conductive organic polymer proton battery provided by this invention achieves good electrochemical performance in the absence of any electrolyte, showcasing the superior proton transport channels of the all-solid-state proton membrane.

[0090] like Figure 6 The image shows an all-solid-state conductive polyaniline symmetric proton cell at 0.1 A·g -1 The cycle performance test results at a certain rate were obtained when the battery's charge / discharge current was 0.1 A·g. -1 At that time, the reversible specific capacity of the battery was approximately 282 mAh·g. -1 After 500 cycles, the reversible specific capacity of the battery increased to 289 mAh·g due to full activation. -1 The initial capacity retention rate of 102% and the coulombic efficiency of 100% demonstrate that the all-solid-state conductive polyaniline symmetric proton battery has excellent cycle stability.

[0091] The experimental results of this test example show that the all-solid-state conductive polyaniline symmetric proton battery prepared in Example 1 has the characteristics of long cycle life and excellent rate performance.

[0092] The embodiments described above are only some, not all, of the embodiments of the present invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. The scope of protection of the present invention is determined by the scope claimed in the claims. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

Claims

1. An all-solid-state conductive organic polymer proton battery, characterized by, The application relates to a battery, which comprises a positive electrode, a negative electrode and a full solid-state proton membrane; the positive electrode and the negative electrode each comprise a current collector and an electrode active material layer loaded on the current collector; the electrode material of the current collector is a graphene felt; the electrode active material layer comprises conductive organic polymer, macromolecular hyperdispersant and polyvinyl alcohol in a mass ratio of (6.75-7.5):(0.75-1.5):(1-2.5); the conductive organic polymer is a nanocomposite material formed by polyaniline and graphene, and the mass ratio of the polyaniline and the graphene is 9:1; the full solid-state proton membrane is a polymer / inorganic hybrid membrane formed by polyvinyl alcohol, nano-silica sol and phosphoric acid under room temperature conditions; the solid mass ratio of the polyvinyl alcohol and the nano-silica sol is 1:1-1:3; and the nano-silica sol is nano-silica sol modified by trimethylsilane ethyl acetate and gamma-glycidyl ether oxypropyl trimethoxysilane.

2. The method for preparing an all-solid-state conductive organic polymer proton battery as described in claim 1, characterized in that, The application further relates to a preparation method of the battery, which comprises the following steps: Step 1) uniformly mixing conductive organic polymer, macromolecular hyperdispersant and polyvinyl alcohol in a proportion to prepare electrode active material coating; then uniformly coating the prepared electrode active material coating on a current collector, drying in an 80 DEG C oven for 4 h, and obtaining an electrode; Step 2) uniformly mixing polyvinyl alcohol, nano-silica sol and phosphoric acid in a proportion under room temperature conditions to prepare a proton membrane solution; then casting the prepared proton membrane solution on a mold, drying at room temperature until the weight is constant, and obtaining a polymer / inorganic hybrid membrane; Step 3) using the electrode prepared in step 1) as the positive electrode and the negative electrode respectively, and using the polymer / inorganic hybrid membrane prepared in step 2) to separate the positive electrode and the negative electrode, and assembling a battery.

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