A full gel battery and its preparation method and application

Abstract

The present invention provides a full gel battery and a preparation method and application thereof. The full gel battery of the present invention comprises a gel electrolyte and electrodes arranged in intervals inside the gel electrolyte. While the electrodes are completely wrapped by the gel electrolyte, the interval arrangement enables the gel electrolyte to also serve as a diaphragm. The full wrapping structure allows the electrodes to fully contact with the electrolyte, which is more in line with the use scenario of the flexible battery.

Description

Technical Field

[0001] The invention belongs to the technical field of batteries, and in particular relates to a full gel battery and a preparation method and application thereof. Background Art

[0002] Aqueous rechargeable zinc-ion batteries are considered to be a potential choice for large-scale energy storage due to their eco-friendly, abundant reserves, high safety and low cost. Currently, lithium-ion batteries occupy most of the energy storage market, and their market share is still growing exponentially. However, expensive raw materials and flammable electrolytes limit the further development and large-scale storage applications of lithium batteries. Promising rechargeable aqueous zinc-ion batteries are currently alternatives to lithium-ion batteries. With the continuous development of energy storage technology and the growing demand, wearable devices are gradually integrated into people's daily lives. One of the keys to the widespread application of these flexible electronic devices is flexible batteries. Flexible zinc-ion batteries have the advantages of low cost, high safety, and high theoretical capacity (820mAh / g). They are easy to assemble and can maintain stable electrochemical properties when bent, folded, twisted and stretched. They are widely used in electronic products, medical implants and wearable devices.

[0003] Many studies have shown that nickel-based materials have high conductivity, excellent redox properties and small band gap energy, and can be used as high-performance positive electrode materials for flexible zinc-ion rechargeable zinc-ion batteries. Metallic zinc negative electrodes have the advantages of non-toxicity, high content, safety and low cost. However, the presence of zinc dendrites greatly affects the cycle stability of liquid electrolyte batteries. In order to solve the above problems, people have made great efforts. The relevant technology shows that the use of polymer gel electrolytes can effectively inhibit the growth of zinc dendrites. However, polymer electrolytes still have the problems of poor interface contact, low ionic conductivity and lower capacity than water-based electrolyte batteries, which greatly limits the further development of flexible aqueous rechargeable zinc-ion batteries. The relevant technology discloses a hydrogel polymer as the matrix material of the battery separator and electrolyte, and a combination of flexible carbon fiber cloth and cobalt-based metal organic framework derivatives (NC / CTs) as the electrode self-supporting current collector and active material support, and then directly grows Ni(OH) on the surface of NC. 2 Nanosheets and ɑ-Fe 2 O 3 Nanorods are used as positive and negative electrodes respectively, and finally two self-supporting flexible electrodes are assembled together with polymer hydrogel electrolyte to form a quasi-sandwich solid-state nickel-iron battery. The battery designed is a sandwich structure gel that only acts as an electrolyte / diaphragm, and the preparation method used in most related technologies uses a high-temperature annealing process, which may cause energy waste. Therefore, it is important to develop polymer electrolytes with excellent interface contact mechanical flexibility, high durability and low interface impedance for flexible zinc-ion batteries. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the first aspect of the present invention proposes a full gel battery, the structure of the battery fully wrapped in gel can make the electrode material fully contact with the electrolyte, and can also meet the use scenario requirements of fitting a flexible body.

[0005] The second aspect of the present invention provides a method for preparing a full gel battery.

[0006] The third aspect of the present invention proposes an application of a full gel battery.

[0007] According to a first aspect of the present invention, a full gel battery is provided, comprising a gel electrolyte and electrodes spaced apart inside the gel electrolyte.

[0008] In the present invention, the electrodes are spaced inside the gel electrolyte, that is, the electrodes are completely wrapped by the gel electrolyte, and the spacing arrangement allows the gel electrolyte to also serve as a separator. The fully wrapped structure allows the electrodes to fully contact the electrolyte, which is more suitable for the use scenario of the flexible battery.

[0009] In some embodiments of the present invention, the thickness of the interval is 1 mm to 5 mm, preferably 1 mm to 3 mm.

[0010] In some preferred embodiments of the present invention, the gel electrolyte comprises a double network gel and an electrolyte.

[0011] In some more preferred embodiments of the present invention, the double network gel comprises unsaturated monomers free radically polymerized in the presence of a crosslinking agent to form a first network and divalent metal ions coordinated and complexed with sodium alginate to form a second network.

[0012] In some more preferred embodiments of the present invention, the unsaturated monomer includes at least one of acrylamide, acrylic acid, and potassium acrylate.

[0013] In some more preferred embodiments of the present invention, the crosslinking agent includes at least one of N,N'-methylenebisacrylamide, pentaerythritol triacrylate, pentaerythritol triethyl ester or polyethylene glycol diacrylate.

[0014] In some more preferred embodiments of the present invention, the ratio of the molar amount of the crosslinking agent to the molar amount of the unsaturated monomer is 0.02% to 0.40%.

[0015] In some more preferred embodiments of the present invention, the divalent metal ions include Zn 2+ , Ca 2+ Any one of .

[0016] In some more preferred embodiments of the present invention, the molar ratio of the divalent metal ion to the sodium alginate is 1:(1-5).

[0017] In some more preferred embodiments of the present invention, the electrolyte includes KOH; the molar concentration of KOH is 1 mol / L to 6 mol / L.

[0018] In some more preferred embodiments of the present invention, the electrode comprises a positive electrode and a negative electrode.

[0019] In some more preferred embodiments of the present invention, the positive electrode comprises a conductive substrate and a positive electrode material modified on the conductive substrate; preferably, the loading amount of the positive electrode material on the conductive substrate is 1 mg / cm 2 ~6mg / cm 2 ; preferably 3mg / cm 2 ~5mg / cm 2 .

[0020] In some more preferred embodiments of the present invention, the conductive substrate comprises one or more of carbon fiber, carbon cloth, metal foil, flexible porous metal and foam metal; the positive electrode material comprises Ni 3 S 2 、NiCo 2 O 4 , any one of NiO.

[0021] In some more preferred embodiments of the present invention, the surface of the positive electrode is also modified with a conductive polymer film; preferably, the conductive polymer film is selected from any one of polyethylene dioxythiophene (PEDOT) film, poly (3,4-ethylene dioxythiophene) - polystyrene sulfonic acid (PEDOT / PSS) film, polyvinylidene fluoride (PVDF) film, polytetrafluoroethylene (PTFE) film; preferably, the positive electrode is immersed in the conductive polymer solution, and after drying, a positive electrode with a surface modified with a conductive polymer film is obtained; further preferably, the solvent of the conductive polymer solution includes an organic solvent and water, and the water volume content is 80% to 99%, preferably 85% to 99%, and the organic solvent includes ethanol and ethylene glycol; further preferably, the immersion time is 8h to 12h; further preferably, the drying temperature is 50°C to 100°C. Modifying the conductive polymer film on the surface of the positive electrode can prevent the material from falling off during the electrochemical cycle.

[0022] In some more preferred embodiments of the present invention, the negative electrode comprises any one of a zinc plate, a zinc sheet, a zinc foil, a zinc foam, metallic zinc particles, a zinc-based alloy or a zinc composite.

[0023] According to a second aspect of the present invention, a method for preparing a full gel battery is provided, comprising the following steps:

[0024] After the first electrode is arranged on the first gel layer, the second gel layer is coated, the second electrode is arranged, and the third gel layer is coated, and then immersed in a solution containing divalent metal ions and electrolyte to obtain the full gel battery.

[0025] In some embodiments of the present invention, the thickness of the gel layer is 1 mm to 3 mm.

[0026] In some preferred embodiments of the present invention, the gel layer comprises unsaturated monomers that are free radical polymerized under a crosslinking agent to form a first network and sodium alginate. After immersion, the sodium alginate in the gel layer forms a second network with divalent metal ions in a solution containing divalent metal ions.

[0027] In some more preferred embodiments of the present invention, the method for preparing the gel layer comprises: adding an unsaturated monomer, a cross-linking agent, an initiator and an accelerator to a sodium alginate solution, mixing and curing at 20° C. to 35° C. to obtain the gel layer.

[0028] In some more preferred embodiments of the present invention, the initiator includes at least one of potassium persulfate and ammonium persulfate.

[0029] In some more preferred embodiments of the present invention, the ratio of the molar amount of the initiator to the molar amount of the unsaturated monomer is 0.01% to 0.05%.

[0030] In some more preferred embodiments of the present invention, the accelerator comprises tetramethylethylenediamine.

[0031] In some more preferred embodiments of the present invention, the ratio of the molar amount of the accelerator to the molar amount of the unsaturated monomer is 0.1% to 0.5%.

[0032] In some more preferred embodiments of the present invention, the soaking time is 6 hours to 12 hours.

[0033] In some more preferred embodiments of the present invention, the molar concentration of the solution containing divalent metal ions is 0.1 mol / L to 0.3 mol / L.

[0034] According to a third aspect of the present invention, an application of the full gel battery in medical implants and wearable devices is proposed.

[0035] The beneficial effects of the present invention are:

[0036] 1. In the present invention, a polymer film with an adhesive effect is attached to the electrode surface by an immersion method to prevent the electrode material from falling off during the electrochemical reaction, thereby further improving the cycle stability.

[0037] 2. In the present invention, the electrodes are completely wrapped by the gel electrolyte, and the interval arrangement allows the gel electrolyte to also serve as a separator. The fully wrapped structure allows the electrodes to fully contact with the electrolyte, which is more suitable for the use scenario of flexible batteries.

[0038] 3. The use of gel electrolyte in the present invention can prevent leakage and prevent the continuous growth of Zn dendrites from piercing the diaphragm and causing short circuit and leakage problems of the battery.

[0039] 4. The preparation method of the full gel battery of the present invention is simple and easy to implement, does not involve a high temperature annealing process, reduces energy loss, and can achieve excellent cycle stability, which is better than most batteries of the same type.

[0040] 5. The full gel battery of the present invention can wrap the electrode material in all directions, provide physical support for the active material, and improve the utilization rate of the active material compared with the traditional sandwich structure capacitor. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] The present invention will be further described below with reference to the accompanying drawings and embodiments, wherein:

[0042] Figure 1 It is a schematic structural diagram of the full gel battery of the present invention.

[0043] Figure 2 This is a schematic diagram of the structure of a sandwich structure gel electrolyte battery in Comparative Example 1 of the present invention.

[0044] Figure 3 The cyclic voltammetry curves of the batteries of Example 3 and Comparative Example 1 in Experimental Example 1 of the present invention at a scan rate of 10 mV / s are shown.

[0045] Figure 4 The graphs are the cycle stability and coulombic efficiency of aqueous batteries of Comparative Examples 2 and 3 in Experimental Example 2 of the present invention.

[0046] Figure 5 Ni in Example 3 of the present invention 3 S 2 / Ni@PEDOT:PSS / / DNGE / / Zn battery cycling stability and Coulombic efficiency diagram.

[0047] Figure 6 The aqueous electrolyte Ni of the comparative example 3 of the present invention is 3 S 2 Plot of cycling stability and coulombic efficiency of / Ni@PEDOT:PSS / / Zn batteries.

[0048] Figure 7 Ni in Example 3 of the present invention 3 S 2 Comparison of the cycling stability of / Ni@PEDOT:PSS / / DNGE / / Zn battery and other similar batteries.

[0049] Figure 8 Ni in Example 3 of the present invention 3 S 2 / Ni@PEDOT:PSS / / DNGE / / Zn battery constant current charge and discharge diagram.

[0050] Fig. 9 Ni in Example 3 of the present invention 3 S 2 / Ni@PEDOT:PSS / / DNGE / / Zn battery adhesion to human tissue application diagram.

[0051] Fig.10 Ni in Example 3 of the present invention 3 S 2 / Ni@PEDOT:PSS / / DNGE / / Zn battery adhesion, bending and conforming to human tissue application diagram.

[0052] Fig.11 Ni in Example 3 of the present invention 3 S 2 / Ni@PEDOT:PSS / / DNGE / / Zn battery application schematic. DETAILED DESCRIPTION

[0053] The following will be combined with the embodiments to clearly and completely describe the concept of the present invention and the technical effects produced, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are all within the scope of protection of the present invention.

[0054] Figure 1 Schematic diagram of the full gel battery of the present invention.

[0055] The preparation methods of the components in the following embodiments or comparative examples are as follows:

[0056] The positive electrode was prepared by ultrasonically cleaning nickel foam (2 cm × 5 cm × 1 mm) with 3 mol / L hydrochloric acid, ethanol and ultrapure water for 30 minutes. 2 S 2 O 3 ·5H 2O was dissolved in 70 mL of deionized water. 2 S 2 O 3 Add 80 μL of HO to the solution. 2 O 2 To accelerate S 2- The obtained solution and the cleaned nickel foam were quickly transferred to a 100 mL autoclave for hydrothermal reaction at 130 °C for 2 h. After the reaction, the Ni 3 S 2 / Ni.

[0057] Ni 3 S 2 / Ni was immersed in a water content (80% to 99%) PEDOT:PSS / ethanol solution for 8h to 12h, and then dried at 60°C. 3 S 2 Ni on PEDOT / Ni@PSS composites 3 S 2 The nanorod loading is about 3.84 mg cm -2 .

[0058] Poly(acrylamide (AM)-potassium acrylate (PA)) / sodium alginate (SA)-Zn 2+ Synthesis of double network gel electrolyte: 3.25g AM, 15g SA (0.06mol / L) and 1.8g PA were dissolved in 2.5g water, and then 5mg NN-methylenebisacrylamide (MBAA), 14mg potassium persulfate (KPS) and 0.125g tetramethylethylenediamine (TMEDA) were added to the above solution, stirred rapidly, and spontaneous polymerization was carried out at room temperature. After assembling into a battery, it was immersed in a Zn-containing 2+ The second layer network structure is formed in the solution.

[0059] The preparation method of the full gel battery is as follows: assemble the full gel flexible battery by layer-by-layer polymerization. Spread a thin layer of gel solution (thickness 2mm) on the bottom, place a positive electrode sheet on the gel layer, and then apply a thin layer of gel solution (thickness 2mm), then place a negative electrode sheet on the surface and apply a thin layer of gel solution (thickness 2mm). Figure 1 As shown in the figure, a battery completely covered with gel was obtained. The battery was immersed in 6 mol / L KOH or 1 mol / L KOH and 0.2 mol / L Zn(CH 3 COO 2 Overnight for further testing.

[0060] Example 1

[0061] This embodiment prepares a full gel battery, and the specific process is as follows:

[0062] Use 2x0.5cm -2 Ni 2 Co 2 O 4 As positive electrode material, 2x0.5cm -2 Zn sheet as negative electrode material, P(AM-PA) / SA-Zn 2+ Gel electrolyte group Figure 1 Pretend to be Ni 2 Co 2 O 4 / / Zn fully gel-coated battery.

[0063] Example 2

[0064] This embodiment prepares a full gel battery, and the specific process is as follows:

[0065] Use 2x0.5cm -2 Ni foam as positive electrode material, 2x0.5cm -2 Zn sheet as negative electrode material, P(AM-PA) / SA-Zn 2+ Gel electrolyte group Figure 1 Assembled into Ni / / Zn full gel encapsulated battery.

[0066] Example 3

[0067] This embodiment prepares a full gel battery, and the specific process is as follows:

[0068] Use 2x0.5cm -2 Ni 3 S 2 / Ni@PEDOT:PSS as cathode material, 2x0.5cm -2 Zn sheet as negative electrode material, P(AM-PA) / SA-Zn 2+ Gel electrolytes, such as Figure 1 Ni was assembled by layer-by-layer polymerization 3 S 2 / Ni@PEDOT:PSS / / Double Network Gel Electrolyte (DNGE) / / Zn Battery.

[0069] Comparative Example 1

[0070] This comparative example prepares a sandwich structure gel battery, which is different from the embodiment in that the battery structure is different. The specific process is as follows:

[0071] Use 2x0.5cm -2 Ni 3 S 2 / Ni@PEDOT:PSS as cathode material, 2x0.5cm -2 Zn sheet is used as negative electrode material, and 2mm P(AM-PA) / SA-Zn is used in the middle 2+ Gel electrolyte, such as Figure 2 Ni assembled into a sandwich structure 3 S 2 @PEDOT:PSS / / Zn battery.

[0072] Comparative Example 2

[0073] This comparative example prepares an alkaline battery, which is different from Example 3 in that the electrolyte is 6 mol / L KOH and 0.2 mol / L Zn(CH 3 COO 2 Aqueous solution, the electrode material is unmodified Ni 3 S 2 / Ni, the specific process is:

[0074] Use 2x0.5cm -2 Ni 3 S 2 / Ni as positive electrode material, 2x0.5cm -2 Zn sheet was used as negative electrode material, 6 mol / L KOH and 0.2 mol / L Zn(CH 3 COO 2 Aqueous solution is used as electrolyte to assemble alkaline batteries.

[0075] Comparative Example 3

[0076] This comparative example prepares an alkaline battery, which is different from Example 3 in that the electrolyte is 6 mol / L KOH and 0.2 mol / L Zn(CH 3 COO 2 Aqueous solution, the specific process is:

[0077] Use 2x0.5cm -2 Ni 3 S 2 / Ni@PEDOT:PSS as cathode material, 2x0.5cm -2 Zn sheet as negative electrode material, 6mol / L KOH and 0.2mol / L Zn(CH3COO) 2 The aqueous solution is used as the electrolyte in the electrolytic cell to assemble into an aqueous alkaline battery.

[0078] Test Example 1

[0079] This test example tests the electrochemical performance of the batteries of Example 3 and Comparative Example 1, and the specific process is as follows:

[0080] The test was performed on a CHI 760E workstation (Shanghai Chenhua Instrument Co., Ltd.) using the same scanning speed of 10 mV / s and the same voltage range of 1.4 V to 2.0 V. 3 S 2 / Ni@PEDOT:PSS battery and the sandwich structure Ni in Comparative Example 1 3 S 2 @PEDOT:PSS battery comparison CV curve Figure 3 As shown. It can be seen that under the same conditions, the full gel Ni 3 S 2 The CV area of ​​the / Ni@PEDOT:PSS full gel battery is larger and the capacity is higher, which proves that the design of the full gel battery makes full use of the electrochemical active materials.

[0081] Test Example 2

[0082] This test example tests the electrochemical performance of the batteries of Comparative Example 2 and Comparative Example 3, and the specific process is as follows:

[0083] The effective area is 1×1cm -2 Ni 3 S 2 / Ni@PEDOT:PSS / / Zn battery and Ni 3 S 2 / Ni / / Zn aqueous alkaline battery, the electrolyte is 6mol / L KOH and 0.2mol / L Zn(CH 3 COO 2 Aqueous solution. The test was carried out in an electrolytic cell using a multi-channel battery test system from Shenzhen Xinwei Electronics Co., Ltd. at 30 mA / cm -2 The current density was 1.4V~2.0V, and 5000 cycles of constant current charge and discharge test were performed. Figure 4 shown.

[0084] from Figure 4 It can be seen that the battery prepared in comparative example 2 has a capacity retention rate of 60% after 5000 cycles at 30 mA / cm, and the battery prepared in comparative example 3 has a capacity retention rate of 85% after 5000 cycles at 30 mA / cm, indicating that the binder layer on the surface of the positive electrode material can enhance the cycle stability of the positive electrode material.

[0085] Test Example 3

[0086] This test example tests the electrochemical performance of the batteries of Example 3 and Comparative Example 3, and the specific process is as follows:

[0087] The effective area is 1×1cm -2The batteries of Example 3 and Comparative Example 3 were tested using a multi-channel battery test system of Shenzhen Neware Electronics Co., Ltd. in an electrolytic cell, at a current density of 30 mA / cm -2 and a voltage range of 1.4 V to 2.0 V for 10,000 cycles of constant current charge and discharge tests. The results are as shown in Figure 5 and Figure 6 .

[0088] It can be seen from Figure 5 that the capacity retention rate of the battery prepared in Example 3 was 88.96% after 10,000 cycles under the condition of 30 mA / cm -2 . It can be seen from Figure 6 that the capacity retention rate of the battery prepared in Comparative Example 3 was 85% after 5,000 cycles under the condition of 30 mA / cm -2 . It is proved that the use of the gel electrolyte in the all-gel of the present invention can inhibit the continuous growth of Zn dendrites, thereby improving the cycle stability. At the same time, the all-gel battery of the present invention can completely wrap the electrode material, provide physical support for the active material, and prevent the active material from falling off into the electrolyte.

[0089] Furthermore, compared with the related technologies (Chen H, Shen Z, Pan Z, Kou Z, Liu X, Zhang H, Gu Q, Guan C, Wang J, Hierarchical micro-nano sheet arrays of nickel-cobalt double hydroxides for high-rate Ni-Zn batteries, Adv Sci. 6(2019)1802002. https: / / doi.org / 10.1002 / advs.201802002. for NiCo-90 / / Zn(850 73%); Wang X, Yang Z, Zhang P, He Y, Qiao Z-A, Zhai X, Huang H, Ni(OH) 2 cathode with oxygen vacancies induced from electroxidizing Ni 3 S 2 nanosheets for aqueous rechargeable Ni-Zn battery, Journal of Alloys and Compounds. 855(2021)https: / / doi.org / 10.1016 / j.jallcom.2020.157488. for Ni 3 S 2 / Ov-Ni(OH) 2 / / Zn(3000 93.2%); Shi W, Mao J, Xu X, Liu W, Zhang L, Cao X, Lu X, An ultra-dense NiS 2 / reduced graphene oxide composite cathode for high-volumetric / gravimetric energy density nickel-zinc batteries, J.Mater.Chem.A. 7(2019)15654-15661. https: / / doi.org / 10.1039 / c9ta04900b. In HD-NiS 2 / rGO-5 / / Zn(2000 80.5%); Cui Z, Shen S, Yu J, Si J, Cai D, Wang Q, Electrospun carbon nanofibers functionalized with NiCo 2 S 4 nanoparticles as lightweight, flexible and binder-free cathode for aqueous Ni-Zn batteries, Chem.Eng.J. 426(2021) https: / / doi.org / 10.1016 / j.cej.2021.130068. In CNF@NiCo 2 S 4 / / Zn(2000 83%); He Y, Zhang P, Huang H, Li X, Zhai X, Chen B, Guo Z, Engineering sulfur vacancies of Ni 3 S 2nanosheets as a binder-free cathode for an aqueous rechargeable Ni-Zn battery,ACS Appl.Energy Mater.3(2020)3863-3875 91.46)Wen J,Feng Z,Liu H,Chen T,Yang Y,LiS,Sheng S,Fang G,In-situ synthesized Ni 2 P nanosheet arrays as the cathode fornovel alkaline Ni / / Zn rechargeable battery,Appl.Surf.Sci.485(2019)462-467 2 P / / Zn(1500 80%)Shi W,Lian J,Fluffy intersected NiCo-OH nanosheet decorated hollow Cu(OH) 2 nanotubearrays on cu foam for high-performance Ni-Zn batteries,Journal of Solid StateChemistry.290(2020)https: / / doi.org / 10.1016 / j.jssc. 2@NiCo–OH / / Zn(3000 100%); Xuan X, Qian M, Pan L, Lu T, Gao Y, Han L, Wan L, Niu Y, Gong S, A hollow tubular NiCo layered double hydroxide@Ag nanowire structure for high-power-density flexible aqueous Ni / / Zn battery, Journal of Energy Chemistry. (2021) https: / / doi.org / 10.1016 / j.jechem.2021.12.013. In LDH@Ag1.5NW&MWCNT(5000 75.9%); Li L, Xiao R, Tao X, Wu Y, Jiang L, Zhang Z, Qing Y, Free-standing electrodes via coupling nanostructured Ni-NiO with hierarchical wood carbon for high-performance supercapacitors and Ni-Zn batteries, J.Power Sources. 491(2021) https: / / doi.org / 10.1016 / j.jpowsour.2021.229618. In Ni–NiO / CTW / / Zn(1000 96.5); Li Q, Jing S, Yong Z, Zhang Q, Liu C, Zhu K, Feng Y, Gong W, Yao Y, Towards ultrahigh-energy-density flexible aqueous rechargeable Ni / / Bi batteries: Free-standing hierarchical nanowire arrays core-shell heterostructures system, Energy Storage Materials. 42(2021) 815-825. https: / / doi.org / 10.1016 / j.ensm.2021.08.032. In FAR Ni / / Bi(5000 88.6%); Wu X, Zhang H, Huang KJ, Chen Z, Stabilizing metallic iron nanoparticles by conformal graphitic carbon coating for high-rate anode in Ni-Fe batteries, Nano Lett. 20(2020)1700-1706. https: / / doi.org / 10.1021 / acs.nanolett.9b04867. in Ni / / Fe(2000 87%); Zhang H, Zhang X, Li H, Zhang Y, Zeng Y, Tong Y, Zhang P, Lu X, Flexible rechargeable Ni / / Zn battery based on self-supported NiCo. 2 O 4 nanosheets with high power density and good cycling stability, Green Energy&Environment. 3(2018)56-62. https: / / doi.org / 10.1016 / j.gee.2017.09.003. in NiCo 2 O 4 / / Zn(3500 82.7%); Yao J, Wan H, Chen C, Ji J, Wang N, Zheng Z, Duan J, Wang X, Ma G, Tao L, Wang H, Zhang J, Wang H, Oxygen-defect enhanced anion adsorption energy toward super-rate and durable cathode for Ni-Zn batteries, Nanomicro Lett. 13(2021)167. https: / / doi.org / 10.1007 / s40820-021-00699-z. in Od-CNO@Ni NTs / / Zn(10000 64%)) and the electrochemical performance of the battery in Example 3, the results are as Figure 5 shown.

[0090] From Figure 7 it can be seen that the battery in Example 3 has excellent cycling stability compared with other alkaline batteries of the same type.

[0091] Test Example 4

[0092] This test example tests the electrochemical performance of the battery of Example 3, and the specific process is as follows:

[0093] The effective area is 1×1cm -2 Ni 3 S 2 / Ni@PEDOT:PSS / / DNGE / / Zn battery. The voltage range is 1.4V~2.0V. At a current density of 8mA / cm 2 , 10mA / cm 2 , 15mA / cm 2 , 20mA / cm 2 、30mA / cm 2 , 40mA / cm 2 The constant current charge and discharge test was carried out on the CHI-760 Shanghai Chenhua workstation under the conditions of Figure 8 shown.

[0094] from Figure 8 It can be seen that the battery prepared in Example 3 has a -2 Provides 1.06 mA h cm -2 According to the formula

[0095] C m =I×Δt / m

[0096] C s =I×Δt / S

[0097] C m Mass specific capacity (mAh / g), C s Representative area capacity (mAh / cm 2 ), I represents the discharge current (A), Δt represents the discharge time (h), m represents the mass of the active material (g), and S represents the area of ​​the electrode (cm -2 ).

[0098] Energy density (E, Wh / kg) E = C m ×ΔV, ΔV(V) is the operating voltage 1.7V.

[0099] Power density (P, kW / kg) P = 3.6 × E / Δt

[0100] work out

[0101] Ni 3 S 2 / Ni@PEDOT:PSS / / DNGE / / Zn battery can reach 469.268Wh kg -1 (3.541kw kg -1) and a peak energy density of 17.706 kW kg -1 (126.37Wh kg -1 )’s maximum power density.

[0102] Application Examples

[0103] like Fig. 9 and Fig.10 The Ni prepared in Example 3 is shown 3 S 2 / Ni@PEDOT:PSS / / DNGE / / Zn battery has flexibility and certain adhesion properties, which can adapt to the deformation of human tissue. This all-gel wrapped battery also has application potential, such as Fig.11 The Ni prepared in Example 3 is shown 3 S 2 / Ni@PEDOT:PSS / / DNGE / / Zn battery can light up an LED lamp.

[0104] The above is a detailed description of the embodiments of the present invention, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in the relevant technical field without departing from the purpose of the present invention. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

Claims

1. A full gel battery, characterized in that: It consists of a gel electrolyte and electrodes spaced inside the gel electrolyte; the electrodes include a positive electrode and a negative electrode, the gel electrolyte includes a double network gel and an electrolyte; the surface of the positive electrode is also modified with a conductive polymer film; the electrolyte includes KOH; the positive electrode includes a conductive substrate and a positive electrode material modified on the conductive substrate; the conductive substrate includes one or more of carbon fiber, carbon cloth, metal foil, flexible porous metal and foam metal; the positive electrode material includes any one of Ni3S2, NiCo2O4 and NiO; the negative electrode includes any one of a zinc plate, a zinc sheet, a zinc foil, foamed zinc, metal zinc particles, a zinc-based alloy or a zinc composite.

2. The full gel battery according to claim 1, characterized in that: The thickness of the interval is 1 mm to 5 mm.

3. The full gel battery according to claim 1, characterized in that: The double network gel comprises unsaturated monomers that are free radical polymerized under a crosslinking agent to form a first network and divalent metal ions that are coordinated and complexed with sodium alginate to form a second network.

4. The full gel battery according to claim 3, characterized in that: The unsaturated monomer includes at least one of acrylamide, acrylic acid and potassium acrylate.

5. The full gel battery according to claim 3, characterized in that: The divalent metal ions include Zn 2+ , Ca 2+ Any one of .

6. The full gel battery according to claim 1, characterized in that: The molar concentration of the KOH is 1 mol / L to 6 mol / L.

7. The full gel battery according to claim 6, characterized in that: The loading amount of the positive electrode material on the conductive substrate is 1 mg / cm 2 ~6mg / cm 2 .

8. The full gel battery according to claim 6, characterized in that: The conductive polymer film is selected from any one of polyethylene dioxythiophene film, poly (3,4-ethylene dioxythiophene) -polystyrene sulfonic acid film, polyvinylidene fluoride film and polytetrafluoroethylene film.

9. A method for preparing a full gel battery, characterized in that: The following steps are involved: After the first electrode is arranged on the first gel layer, the second gel layer is coated, the second electrode is arranged, and the third gel layer is coated, and immersed in a solution containing divalent metal ions and an electrolyte to obtain a full gel battery as described in any one of claims 1 to 8.

10. Application of the full gel battery as claimed in any one of claims 1 to 8 in medical implants and wearable devices.

Images