Flexible paper battery and preparation method and application thereof
By using ultrasonic dispersion technology of cellulose materials and conductive materials in flexible paper batteries, combined with traditional papermaking processes, flexible paper batteries with excellent flexibility and electrochemical properties are prepared, solving the problems of high cost and complex production of existing flexible batteries, and achieving efficient and low-cost battery production.
Patent Information
- Application Number
- CN202510075215.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-17
- Publication Date
- 2025-05-23
AI Technical Summary
Existing flexible batteries face problems such as high costs, limited material resources, short bending life of batteries and complex production processes, making it difficult to achieve large-scale and low-cost production.
A flexible paper battery is prepared by ultrasonic dispersing cellulose material, conductive material and active material in deionized water to form a mixed suspension of negative electrode, separator and positive electrode. The traditional papermaking process is used for suction filtration and hot pressing drying treatment, and a flexible paper battery with an integrated structure is prepared.
It realizes excellent mechanical flexibility and electrochemical stability of flexible paper batteries, improves energy density, reduces production costs, and simplifies the preparation process, which is suitable for large-scale production.
Smart Images
Figure CN120033339A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of secondary batteries, and in particular relates to a flexible paper battery and a preparation method and application thereof. Background Art
[0002] With the rapid development of wearable devices, flexible electronic products, smart sensors and other fields, the market demand for lightweight, bendable and environmentally friendly batteries continues to increase. Although traditional rigid batteries perform well in terms of energy density and stability, they are difficult to meet the needs of flexible and convenient use due to their rigid shell, heavy weight and inability to adapt to the characteristics of flexible electronic devices. In order to solve these problems, flexible battery technology came into being, especially in application scenarios such as low-power electronic products and sensors, flexible batteries have become an important research direction.
[0003] At present, most flexible batteries use ultra-thin metals (such as copper, aluminum), conductive polymers, etc. as current collectors and conductive materials. Although they can achieve certain flexibility and electrochemical properties, they face problems such as high cost, limited material resources, and short battery bending life. In particular, the production process of these materials is relatively complicated and the cost is high, making it difficult to achieve large-scale, low-cost production. Therefore, how to develop a battery system with excellent flexibility, good electrochemical properties, and low cost has become an urgent problem to be solved in the current flexible battery field.
[0004] In recent years, paper-based materials (mainly cellulose) have become emerging materials in flexible battery research due to their biodegradability, low cost, light weight and good flexibility. Paper batteries not only have excellent mechanical flexibility and electrochemical properties, but also exhibit low environmental burden, meeting the requirements of green and sustainable development.
[0005] However, existing paper batteries still face bottlenecks such as low energy density, poor cycle stability, and complex production processes. Although some studies have explored the application of paper-based materials in batteries, mature commercial technology has not yet been formed. Therefore, the development of new flexible paper batteries that can improve their electrochemical properties, optimize production processes, and reduce production costs is the key to the development of this field. Summary of the invention
[0006] In view of the problems existing in the prior art, the present invention provides a flexible paper battery and a preparation method and application thereof, and prepares a flexible paper battery with excellent mechanical flexibility and electrochemical stability, which can not only solve the problem that rigid batteries are difficult to mechanically deform, but also further improve the energy density of flexible batteries and reduce production costs; in addition, the preparation process only involves the water environment and has the attribute of green and environmental protection.
[0007] The present invention adopts the following technical solutions to solve the above problems:
[0008] In a first aspect, the present invention provides a method for preparing a flexible paper battery, wherein the method can prepare a flexible paper battery having an integrated structure, and specifically comprises the following steps:
[0009] Step 1: adding a certain mass of cellulose material, conductive material, and negative electrode active material into deionized water for ultrasonic dispersion to obtain a negative electrode mixed suspension A;
[0010] Step 2, adding a certain mass of cellulose material into deionized water, and ultrasonically dispersing to obtain a diaphragm suspension B;
[0011] Step 3, adding a certain mass of cellulose material, conductive material, and positive electrode active material into deionized water for ultrasonic dispersion to obtain a positive electrode mixed suspension C;
[0012] Step 4, referring to the traditional papermaking process, the suspension A, suspension B, and suspension C are filtered in turn, and then the semi-finished product is hot-pressed and dried to obtain a flexible paper battery with an integrated structure.
[0013] Furthermore, in steps 1-3, the cellulose material includes but is not limited to one of wood fiber, grass fiber, cotton fiber, bacterial fiber, algae fiber, and waste paper fiber.
[0014] Furthermore, in step 1 and step 3, the conductive material includes but is not limited to one of conductive carbon black, carbon nanotubes, graphene, metal nanoparticles, polyaniline, and conductive ink.
[0015] Furthermore, in step 1, the negative electrode active material includes but is not limited to one of graphite, silicon-based materials, silicon-carbon composite materials, hard carbon, soft carbon, conductive polymers, zinc powder, and activated carbon.
[0016] Furthermore, in step 3, the positive electrode active material includes but is not limited to one of lithium iron phosphate, lithium cobalt oxide, nickel cobalt manganese oxide, sodium cobalt oxide, sodium manganese oxide, sodium iron phosphate, organic sulfide, potassium cobalt oxide, potassium molybdenum oxide, potassium iron phosphate, manganese dioxide, and activated carbon.
[0017] In a second aspect, the present invention provides a flexible paper battery prepared by the above-mentioned flexible paper battery preparation method.
[0018] Furthermore, the flexible paper battery includes an integrally formed paper-based positive electrode material, a paper-based separator and a paper-based negative electrode material, and flexible packaging materials are provided on the outside of the paper-based positive electrode material and the paper-based negative electrode material.
[0019] In a third aspect, the present invention provides an application of the above-mentioned flexible paper battery, which can be applied to lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, zinc-manganese batteries and supercapacitors.
[0020] Furthermore, when applied to the lithium-ion battery, sodium-ion battery, and potassium-ion battery, the electrolyte is a carbonate or ether electrolyte; when applied to the zinc-manganese battery and supercapacitor, the electrolyte is an aqueous electrolyte.
[0021] Advantages of the present invention:
[0022] 1. The flexible paper battery prepared by the present invention is composed of three layers of functional materials with an integrated structure, wherein the bottom layer is the negative electrode of the paper battery, comprising cellulose material, conductive material and negative electrode active material, ensuring that the negative electrode has sufficient conductivity and electric energy storage characteristics; the middle layer is the paper battery separator, which only comprises cellulose material, and its main function is to ensure ion transmission during charging and discharging and isolate the positive and negative electrodes of the battery to avoid battery short circuit; the top layer is the positive electrode of the paper battery, comprising cellulose material, conductive material and positive electrode active material, ensuring that the positive electrode has sufficient conductivity and electric energy storage characteristics. The above characteristics give the flexible paper battery excellent mechanical flexibility while ensuring the electrochemical performance of the battery. When the flexible paper battery is combined with flexible electrical equipment, it exhibits excellent structural stability.
[0023] 2. The prepared flexible paper battery exhibits excellent electrochemical properties and mechanical flexibility due to its integrated structure. The internal components of the battery are integrated, which improves the structural stability of the flexible paper battery and simplifies the battery preparation process.
[0024] 3. The flexible paper battery prepared by the present invention can be customized in shape and size according to the electrical equipment, providing more options for the design and manufacture of flexible electrical equipment.
[0025] 4. The preparation method of the present invention draws on the traditional papermaking process, mainly involving low-cost raw materials (including cellulose materials, carbon-based materials, commercial electrode active materials) and simple operating procedures (including filtration and hot pressing and drying), which can achieve continuous production and lay the foundation for the practical application of flexible electrical equipment. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] In order to more clearly illustrate the specific embodiments of the present invention, the drawings required for use in the description of the specific embodiments will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0027] Figure 1 This is a schematic diagram of the flexible lithium-ion paper battery obtained in Example 1 of the present invention;
[0028] Figure 2This is a scanning electron microscope (SEM) image of the bottom (negative electrode) of the flexible paper battery obtained in Example 1 of the present invention;
[0029] Figure 3 This is a SEM image of the top (positive electrode) of the flexible paper battery obtained in Example 1 of the present invention;
[0030] Figure 4 This is an X-ray diffraction (XRD) diagram of the flexible paper battery obtained in Example 1 of the present invention;
[0031] Figure 5 The discharge capacity retention rate and coulombic efficiency diagram of the flexible paper battery obtained in Example 1 of the present invention after 100 cycles at a current density of 1C;
[0032] Figure 6 These are photos of the flexible paper battery obtained in Example 1 of the present invention at different bending angles;
[0033] Figure 7 This is a graph showing the capacity retention rate of the flexible paper battery obtained in Example 1 of the present invention at different bending angles;
[0034] Figure 8 This is a diagram of the flexible paper battery obtained in Example 1 of the present invention being used to power a flexible LED. DETAILED DESCRIPTION
[0035] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is described in detail below with reference to the accompanying drawings and specific embodiments.
[0036] The present invention provides a method for preparing a flexible paper battery, which can prepare a flexible paper battery with an integrated structure, and specifically comprises the following steps:
[0037] Step 1: adding a certain mass of cellulose material, conductive material, and negative electrode active material into deionized water for ultrasonic dispersion to obtain a negative electrode mixed suspension A;
[0038] Step 2, adding a certain mass of cellulose material into deionized water, and ultrasonically dispersing to obtain a diaphragm suspension B;
[0039] Step 3, adding a certain mass of cellulose material, conductive material, and positive electrode active material into deionized water for ultrasonic dispersion to obtain a positive electrode mixed suspension C;
[0040] Step 4, referring to the traditional papermaking process, suspension A, suspension B, and suspension C are filtered in turn, and then the semi-finished product is hot-pressed and dried to obtain a flexible paper battery with an integrated structure.
[0041] In the above steps, the cellulose material includes but is not limited to one of wood fiber, grass fiber, cotton fiber, bacterial fiber, algae fiber, and waste paper fiber; the conductive material includes but is not limited to one of conductive carbon black, carbon nanotubes, graphene, metal nanoparticles, polyaniline, and conductive ink; the negative electrode active material includes but is not limited to one of graphite, silicon-based materials, silicon-carbon composites, hard carbon, soft carbon, conductive polymers, zinc powder, and activated carbon; the positive electrode active material includes but is not limited to one of lithium iron phosphate, lithium cobalt oxide, nickel cobalt manganese oxide, sodium cobalt oxide, sodium manganese oxide, sodium iron phosphate, organic sulfide, potassium cobalt oxide, potassium molybdenum oxide, potassium iron phosphate, manganese dioxide, and activated carbon.
[0042] Example 1
[0043] In this embodiment, the cellulose material is bamboo pulp fiber, the conductive material is multi-walled carbon nanotubes, the negative electrode active material is graphite, and the positive electrode active material is lithium iron phosphate. The specific steps include:
[0044] Step 1: add 471 mg of bamboo pulp fiber, 471 mg of multi-walled carbon nanotubes and 942 mg of graphite into 500 mL of deionized water, and continue mechanical stirring for standby use to obtain a negative electrode mixed suspension A.
[0045] Step 2, adding 942 mg of bamboo paddle fiber into 300 mL of deionized water, and continuously stirring mechanically for standby use to obtain a diaphragm suspension B.
[0046] Step 3, add 471 mg of bamboo pulp fiber, 628 mg of multi-walled carbon nanotubes and 2562 mg of lithium iron phosphate powder into 500 mL of deionized water, continue mechanical stirring for standby use, and obtain a positive electrode mixed suspension C.
[0047] Step 4, referring to the traditional papermaking process, the negative electrode mixed suspension A, the diaphragm suspension B and the positive electrode mixed suspension C are filtered in turn, and then the obtained integrated material containing water is hot-pressed and dried to obtain a flexible lithium-ion paper battery.
[0048] like Figure 1 As shown, the thin black lines represent multi-walled carbon nanotubes, the thick gray lines represent bamboo pulp fibers, and the granular substances at the top and bottom represent the positive electrode active materials and the negative electrode active materials, respectively.
[0049] according to Figure 2 It can be seen from the SEM image that the bamboo pulp fibers, multi-walled carbon nanotubes and graphite are evenly distributed in the flexible paper battery obtained in this embodiment.
[0050] according to Figure 3 It can be seen from the SEM image that the bamboo pulp fibers, multi-walled carbon nanotubes and lithium iron phosphate are evenly distributed in the flexible paper battery obtained in this embodiment.
[0051] according to Figure 4 From the XRD comparison, it can be seen that the process of preparing flexible paper batteries through traditional papermaking process will not affect the electrode active materials.
[0052] according to Figure 5 It can be seen that after 100 charge and discharge cycles at a current density of 1C, the capacity retention rate of the flexible paper battery obtained in this embodiment is about 95%.
[0053] according to Figure 6 and 7 It can be seen that the capacity retention rates of the flexible paper battery obtained in this embodiment are 96%, 91% and 88% respectively when bent at 60°, 120° and 180°, showing excellent electrochemical performance and mechanical flexibility.
[0054] according to Figure 8 It can be seen that the flexible paper battery obtained in this embodiment can stably drive the flexible LED in a bent state, demonstrating the excellent practical potential of the flexible paper battery.
[0055] Example 2
[0056] In this embodiment, the cellulose material is bamboo pulp fiber, the conductive material is multi-walled carbon nanotubes, the negative electrode active material is hard carbon, and the positive electrode active material is sodium vanadium phosphate. The specific steps include:
[0057] Step 1: add 471 mg of bamboo pulp fiber, 471 mg of multi-walled carbon nanotubes and 600 mg of hard carbon into 500 mL of deionized water, and continue mechanical stirring for standby use to obtain a negative electrode mixed suspension A.
[0058] Step 2, adding 942 mg of bamboo paddle fiber into 300 mL of deionized water, and continuously stirring mechanically for standby use to obtain a diaphragm suspension B.
[0059] Step 3, add 471 mg of bamboo pulp fiber, 628 mg of multi-walled carbon nanotubes and 2045 mg of sodium vanadium phosphate into 500 mL of deionized water, continue mechanical stirring for standby use, and obtain a positive electrode mixed suspension C.
[0060] Step 4, referring to the traditional papermaking process, the negative electrode mixed suspension A, the diaphragm suspension B and the positive electrode mixed suspension C are filtered in turn, and then the obtained integrated material containing water is hot-pressed and dried to obtain a flexible sodium ion paper battery.
[0061] Example 3
[0062] In this embodiment, the cellulose material is bamboo pulp fiber, the conductive material is multi-walled carbon nanotubes, the negative electrode active material is hard carbon, and the positive electrode active material is potassium iron phosphate. The specific steps include:
[0063] Step 1: add 471 mg of bamboo pulp fiber, 471 mg of multi-walled carbon nanotubes and 600 mg of hard carbon into 500 mL of deionized water, and continue mechanical stirring for standby use to obtain a negative electrode mixed suspension A.
[0064] Step 2, adding 942 mg of bamboo paddle fiber into 300 mL of deionized water, and continuously stirring mechanically for standby use to obtain a diaphragm suspension B.
[0065] Step 3, add 471 mg of bamboo pulp fiber, 628 mg of multi-walled carbon nanotubes and 1050 mg of potassium iron phosphate into 500 mL of deionized water, continue mechanical stirring for standby use, and obtain a positive electrode mixed suspension C.
[0066] Step 4, referring to the traditional papermaking process, the negative electrode mixed suspension A, the diaphragm suspension B and the positive electrode mixed suspension C are filtered in turn, and then the obtained integrated material containing water is hot-pressed and dried to obtain a flexible potassium ion paper battery.
[0067] Example 4
[0068] In this embodiment, the cellulose material is bamboo pulp fiber, the conductive material is multi-walled carbon nanotubes, the negative electrode active material is zinc powder, and the positive electrode active material is manganese dioxide. The specific steps include:
[0069] Step 1: add 471 mg of bamboo pulp fiber, 471 mg of multi-walled carbon nanotubes and 500 mg of zinc powder into 500 mL of deionized water, and continue mechanical stirring for standby use to obtain a negative electrode mixed suspension A.
[0070] Step 2, adding 942 mg of bamboo paddle fiber into 300 mL of deionized water, and continuously stirring mechanically for standby use to obtain a diaphragm suspension B.
[0071] Step 3, add 471 mg of bamboo pulp fiber, 628 mg of multi-walled carbon nanotubes and 600 mg of manganese dioxide into 500 mL of deionized water, continue mechanical stirring for standby use, and obtain a positive electrode mixed suspension C.
[0072] Step 4, referring to the traditional papermaking process, the negative electrode mixed suspension A, the diaphragm suspension B and the positive electrode mixed suspension C are filtered in turn, and then the obtained integrated material containing water is hot-pressed and dried to obtain a flexible zinc-manganese paper battery.
[0073] Example 5
[0074] In this embodiment, the cellulose material is bamboo pulp fiber, the conductive material is multi-walled carbon nanotubes, the negative electrode active material is activated carbon, and the positive electrode active material is activated carbon. The specific steps include:
[0075] Step 1: add 471 mg of bamboo pulp fiber, 471 mg of multi-walled carbon nanotubes and 800 mg of activated carbon into 500 mL of deionized water, and continue mechanical stirring for standby use to obtain a negative electrode mixed suspension A.
[0076] Step 2, adding 942 mg of bamboo paddle fiber into 300 mL of deionized water, and continuously stirring mechanically for standby use to obtain a diaphragm suspension B.
[0077] Step 3, add 471 mg of bamboo pulp fiber, 628 mg of multi-walled carbon nanotubes and 800 mg of activated carbon into 500 mL of deionized water, continue mechanical stirring for standby use, and obtain a positive electrode mixed suspension C.
[0078] Step 4, referring to the traditional papermaking process, the negative electrode mixed suspension A, the diaphragm suspension B and the positive electrode mixed suspension C are filtered in turn, and then the obtained integrated material containing water is hot-pressed and dried to obtain a flexible supercapacitor.
[0079] Example 6
[0080] This embodiment provides a flexible paper battery, which is prepared by any of the flexible paper battery preparation methods of Embodiments 1 to 5. Figure 1 As shown, the flexible paper battery includes an integrally formed paper-based positive electrode material, a paper-based separator and a paper-based negative electrode material, and flexible packaging materials are provided on the outside of the paper-based positive electrode material and the paper-based negative electrode material.
[0081] Example 7
[0082] This embodiment provides an application of a flexible paper battery. The flexible paper battery is assembled in the following manner in Embodiments 1 to 5:
[0083] Assembly of lithium-ion battery: The flexible paper battery prepared in Example 1 was cut into 4 cm × 4 cm squares as the battery core. The electrolyte was 1 mol / L lithium hexafluorophosphate, and the solvent was a mixture of ethylene carbonate and diethyl carbonate in a volume ratio of 1:1. The batteries were assembled in an argon glove box.
[0084] Assembly of sodium ion battery: The flexible paper battery prepared in Example 2 was cut into 4 cm × 4 cm squares as the battery core. The electrolyte was 1 mol / L sodium hexafluorophosphate, and the solvent was a mixture of ethylene carbonate and diethyl carbonate in a volume ratio of 1:1. The batteries were assembled in an argon glove box.
[0085] Assembly of potassium ion battery: The flexible paper battery prepared in Example 3 was cut into 4 cm × 4 cm squares as the battery core part, the electrolyte was 1 mol / L potassium hexafluorophosphate, and the solvent was a mixture of ethylene carbonate and diethyl carbonate in a volume ratio of 1:1, and assembled in an argon glove box.
[0086] Assembly of zinc-manganese battery: The flexible paper battery prepared in Example 4 was cut into 4 cm×4 cm squares as the battery core part. The electrolyte was 30% ammonium chloride and the solvent was deionized water. The battery was assembled under air conditions.
[0087] Assembly of supercapacitor: The flexible paper battery prepared in Example 5 was cut into 4 cm×4 cm squares as the core part of the supercapacitor. The electrolyte was 6 mol / L potassium hydroxide and the solvent was deionized water. The assembly was carried out under air conditions.
[0088] The present invention is described in detail above through the embodiments, but the contents are only preferred embodiments of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made according to the scope of application of the present invention should still fall within the scope of the patent coverage of the present invention.
Claims
1. A method for preparing a flexible paper battery, characterized in that: The method can produce a flexible paper battery with an integrated structure, and specifically comprises the following steps: Step 1: adding a certain mass of cellulose material, conductive material, and negative electrode active material into deionized water for ultrasonic dispersion to obtain a negative electrode mixed suspension A; Step 2: adding a certain mass of cellulose material into deionized water and performing ultrasonic dispersion to obtain a membrane suspension B; Step 3: adding a certain mass of cellulose material, conductive material, and positive electrode active material into deionized water for ultrasonic dispersion to obtain a positive electrode mixed suspension C; Step 4: Referring to the traditional papermaking process, the suspension A, suspension B, and suspension C are filtered in turn, and then the semi-finished product is hot-pressed and dried to obtain a flexible paper battery with an integrated structure.
2. The method for preparing a flexible paper battery according to claim 1, characterized in that: In steps 1-3, the cellulose material includes but is not limited to one of wood fiber, grass fiber, cotton fiber, bacterial fiber, algae fiber, and waste paper fiber.
3. The method for preparing a flexible paper battery according to claim 1, characterized in that: In step 1 and step 3, the conductive material includes but is not limited to one of conductive carbon black, carbon nanotubes, graphene, metal nanoparticles, polyaniline, and conductive ink.
4. The method for preparing a flexible paper battery according to claim 1, characterized in that: In step 1, the negative electrode active material includes but is not limited to one of graphite, silicon-based materials, silicon-carbon composite materials, hard carbon, soft carbon, conductive polymers, zinc powder, and activated carbon.
5. The method for preparing a flexible paper battery according to claim 1, characterized in that: In step 3, the positive electrode active material includes but is not limited to one of lithium iron phosphate, lithium cobalt oxide, nickel cobalt manganese oxide, sodium cobalt oxide, sodium manganese oxide, sodium iron phosphate, organic sulfide, potassium cobalt oxide, potassium molybdenum oxide, potassium iron phosphate, manganese dioxide, and activated carbon.
6. A flexible paper battery, characterized in that: The flexible paper battery is prepared by the preparation method of any one of claims 1 to 5.
7. A flexible paper battery according to claim 6, characterized in that: The flexible paper battery comprises an integrally formed paper-based positive electrode material, a paper-based separator and a paper-based negative electrode material, and flexible packaging materials are provided on the outside of the paper-based positive electrode material and the paper-based negative electrode material.
8. An application of the flexible paper battery according to claim 6 or 7, characterized in that: Applied to lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, zinc-manganese batteries and supercapacitors.
9. The application of the flexible paper battery according to claim 8, characterized in that: When applied to the lithium ion battery, sodium ion battery, and potassium ion battery, the electrolyte is a carbonate or ether electrolyte; when applied to the zinc-manganese battery and supercapacitor, the electrolyte is an aqueous electrolyte.