CN113764741B - A kind of flexible paper-based battery and its preparation method - Google Patents
A kind of flexible paper-based battery and its preparation method Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 113
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 53
- 239000000758 substrate Substances 0.000 claims abstract description 40
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052737 gold Inorganic materials 0.000 claims abstract description 31
- 239000010931 gold Substances 0.000 claims abstract description 31
- 229910052709 silver Inorganic materials 0.000 claims abstract description 25
- 239000004332 silver Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 238000009713 electroplating Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 238000005342 ion exchange Methods 0.000 claims abstract description 7
- 238000007772 electroless plating Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 28
- 238000007747 plating Methods 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 4
- 229940038773 trisodium citrate Drugs 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000000123 paper Substances 0.000 claims 10
- 238000002791 soaking Methods 0.000 claims 4
- 238000005406 washing Methods 0.000 claims 3
- 239000011088 parchment paper Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- 238000005246 galvanizing Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VAYOSLLFUXYJDT-RDTXWAMCSA-N Lysergic acid diethylamide Chemical compound C1=CC(C=2[C@H](N(C)C[C@@H](C=2)C(=O)N(CC)CC)C2)=C3C2=CNC3=C1 VAYOSLLFUXYJDT-RDTXWAMCSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
技术领域technical field
本发明涉及柔性电子学领域中的能源器件，包括柔性衬底上的金属生长及其图形化。本发明展示了一种柔性大、工艺方法简单、工艺过程无毒、成本低的柔性纸基电池及其制备方法。The invention relates to energy devices in the field of flexible electronics, including metal growth on a flexible substrate and its patterning. The invention shows a flexible paper-based battery with large flexibility, simple process, non-toxic process and low cost and a preparation method thereof.
背景技术Background technique
随着柔性电子技术的发展，出现了许多基于柔性衬底的器件，例如可穿戴柔性显示屏、分布式传感器、柔性传感器等。电池作为各类电子器件的能量来源，有着巨大的研究意义和广泛的应用，因此柔性电池应运而生。它不仅与半导体制造工艺兼容，并且具有优秀的机械性、弯曲性和可穿戴、可折叠的特点，因此可以满足市场的需求。此外，柔性纸基电极还具备重量轻、易集成、绿色环保等优点。因此，柔性纸电池的应用场景非常广泛。With the development of flexible electronics technology, many devices based on flexible substrates have emerged, such as wearable flexible displays, distributed sensors, flexible sensors, etc. As the energy source of various electronic devices, batteries have great research significance and wide applications, so flexible batteries emerged as the times require. It is not only compatible with the semiconductor manufacturing process, but also has excellent mechanical properties, flexibility, and wearable and foldable features, so it can meet the needs of the market. In addition, flexible paper-based electrodes also have the advantages of light weight, easy integration, and environmental protection. Therefore, the application scenarios of flexible paper batteries are very extensive.
在纸基电池的制备过程中，如中国专利：201821057988.5中公布的一种纸基电池的制备方法，虽然可以达到很高的效率，但其灵活性和环保度以及成本均不够好。这将限制纸电池的批量生产和应用。In the preparation process of paper-based batteries, such as a preparation method of paper-based batteries disclosed in Chinese Patent: 201821057988.5, although high efficiency can be achieved, its flexibility, environmental protection and cost are not good enough. This will limit the mass production and application of paper batteries.
在各类电池中，银锌电池是一种成熟的二次电池系统，在放电过程中能够保持稳定的电压，其典型工作电压为1.5V，可以满足大部分柔性器件的要求。此外，银锌电池无毒、环保，制备过程毒性低，不需要手套箱制备，理论能量密度高达478Wh.kg-1，放电电压较高，满足便携式和可穿戴电子设备的要求，在柔性电池领域具有更大的潜力。Among all kinds of batteries, silver-zinc battery is a mature secondary battery system, which can maintain a stable voltage during discharge. Its typical working voltage is 1.5V, which can meet the requirements of most flexible devices. In addition, silver-zinc batteries are non-toxic and environmentally friendly. The preparation process has low toxicity and does not require glove box preparation. The theoretical energy density is as high as 478Wh.kg -1 , and the discharge voltage is high. It meets the requirements of portable and wearable electronic devices and has greater potential in the field of flexible batteries.
发明内容Contents of the invention
本发明的目的是针对现有技术的不足之处，提供一种柔性纸基电池及其制备方法，可实现在普通滤纸、A4打印纸、硫酸纸等纸基衬底上制备电极，与合适的电解液组合即可构成一种柔性纸基电池，具有电化学稳定性高、粘附性好、介电常数低、热稳定性高、工艺简单、成本低、绿色环保、可降解、重量轻、可回收和易弯曲等优点。The purpose of the present invention is to address the deficiencies of the prior art, to provide a flexible paper-based battery and a preparation method thereof, which can realize the preparation of electrodes on paper-based substrates such as ordinary filter paper, A4 printing paper, sulfuric acid paper, etc., and combine with a suitable electrolyte to form a flexible paper-based battery.
实现本发明目的的具体技术方案是：The concrete technical scheme that realizes the object of the invention is:
一种柔性纸基电池的制备方法，该方法包括以下具体步骤：A method for preparing a flexible paper-based battery, the method comprising the following specific steps:
步骤1：用离子交换法在衬底两端制备金属镍层，具体包括：Step 1: Prepare a metal nickel layer on both ends of the substrate by ion exchange method, specifically including:
（i）用去离子水、乙醇和丙酮分别对衬底进行超声波清洗25～35 min，得到无尘化衬底，烘干；(i) Ultrasonic cleaning of the substrate with deionized water, ethanol and acetone for 25-35 min, respectively, to obtain a dust-free substrate, and drying;
（ii）将清洗烘干的衬底两端分别置于硫酸镍溶液中浸泡10～15min，使得衬底表面进行金属离子吸附；(ii) Soak both ends of the cleaned and dried substrate in nickel sulfate solution for 10-15 minutes, so that metal ions can be adsorbed on the surface of the substrate;
（iii）将步骤（ii）的衬底用去离子水冲洗烘干后，置于硼氢化钠溶液中浸泡3~5min，使表面吸附的金属离子与溶液发生反应，生成镍种子层；(iii) Rinse and dry the substrate in step (ii) with deionized water, and soak in sodium borohydride solution for 3-5 minutes, so that the metal ions adsorbed on the surface react with the solution to form a nickel seed layer;
（iv）将步骤（iii）的衬底用去离子水冲洗烘干后，接着放入商用无电镀镍溶液中浸泡20～30min，得到导电且致密的金属镍层；(iv) Rinse and dry the substrate in step (iii) with deionized water, and then soak it in a commercial electroless nickel plating solution for 20 to 30 minutes to obtain a conductive and dense metallic nickel layer;
步骤2：将步骤1所得的金属镍层用去离子水冲洗烘干后，置于商用无电镀金溶液中浸泡20～30min，在镍层表面无电镀一层金纳米粒子，得到镍/金电极，作为柔性纸基电池的集流体；Step 2: Rinse and dry the metal nickel layer obtained in step 1 with deionized water, soak it in a commercial electroless gold plating solution for 20 to 30 minutes, and electrolessly plate a layer of gold nanoparticles on the surface of the nickel layer to obtain a nickel/gold electrode as a current collector for a flexible paper-based battery;
步骤3：在步骤2所得的镍/金集流体的一端电镀银，具体包括：Step 3: electroplating silver on one end of the nickel/gold current collector obtained in step 2, specifically including:
（ⅰ）配置镀银溶液；(i) Configure the silver plating solution;
（ⅱ）待电镀的集流体作为阴极，银丝作为阳极，放入镀银溶液，在-0.5V电压下电镀10～20min，电沉积制得柔性银电极，作为阴极；(ii) The current collector to be electroplated is used as the cathode, and the silver wire is used as the anode, put into the silver plating solution, electroplate at -0.5V for 10 to 20 minutes, and electrodeposit to obtain a flexible silver electrode as the cathode;
步骤4：在步骤2所得的镍/金集流体另一端电镀锌，具体包括：Step 4: Galvanizing the other end of the nickel/gold current collector obtained in step 2, specifically including:
（ⅰ）配置镀锌溶液；(i) Configure the galvanizing solution;
（ⅱ）待电镀的集流体作为工作电极，铂电极作为对电极，银-氯化银电极作为参比电极，在镀锌溶液中，加-0.8V电压，电镀10～20min，电沉积制得柔性锌电极，作为阳极；(ii) The current collector to be electroplated is used as the working electrode, the platinum electrode is used as the counter electrode, and the silver-silver chloride electrode is used as the reference electrode. In the galvanizing solution, a voltage of -0.8V is applied, and electroplating is performed for 10 to 20 minutes, and a flexible zinc electrode is obtained by electrodeposition as the anode;
步骤5：在步骤3、步骤4所得阳极、阴极上引出导线，滴上电解液，得到所述柔性纸基电池；其中：Step 5: Lead wires on the anode and cathode obtained in Step 3 and Step 4, and drip the electrolyte to obtain the flexible paper-based battery; wherein:
所述衬底为纸质材料，包括A4纸、滤纸和硫酸纸；The substrate is a paper material, including A4 paper, filter paper and sulfuric acid paper;
所述硫酸镍溶液浓度为80~100 mM，温度为80~100℃；The concentration of the nickel sulfate solution is 80 to 100 mM, and the temperature is 80 to 100°C;
所述硼氢化钠溶液浓度为0.03～0.05 M，温度为室温；The concentration of the sodium borohydride solution is 0.03-0.05 M, and the temperature is room temperature;
所述商用无电镀镍溶液的温度为90~120℃；The temperature of described commercial electroless nickel plating solution is 90～120 ℃;
所述商用无电镀金溶液的温度为90~120℃。The temperature of the commercial electroless gold plating solution is 90-120°C.
本发明所述电镀银溶液由0.4M的硝酸银溶液和0.4～0.8M的硝酸钠溶液按1∶1的体积比混合而成。The electroplating silver solution of the present invention is formed by mixing 0.4M silver nitrate solution and 0.4-0.8M sodium nitrate solution according to the volume ratio of 1:1.
本发明所述电镀锌溶液由0.6～0.8M的硫酸锌溶液和1M的柠檬酸三钠溶液按1∶1的体积比混合而成。The electrogalvanizing solution of the invention is prepared by mixing 0.6-0.8M zinc sulfate solution and 1M trisodium citrate solution in a volume ratio of 1:1.
本发明所述电解液为1~5M氯化钠溶液或氯化锂溶液；所述镀锌液包含所有可以用于电镀的锌盐，例如氯化锌等；所述电解液包含所有适用于银锌电池的电解液。The electrolyte of the present invention is 1-5M sodium chloride solution or lithium chloride solution; the zinc plating solution contains all zinc salts that can be used for electroplating, such as zinc chloride; the electrolyte contains all electrolytes suitable for silver-zinc batteries.
一种上述方法制得的柔性纸基电池。A flexible paper-based battery prepared by the above method.
本发明的有益效果：Beneficial effects of the present invention:
本发明相比于其他电池，具有柔性、质量轻、制备工艺简单、成本低的优点，在很多领域具有应用前景。纸基电池是一个新兴领域，本发明具有创新性。Compared with other batteries, the invention has the advantages of flexibility, light weight, simple preparation process and low cost, and has application prospects in many fields. Paper-based batteries are an emerging field, and this invention is innovative.
附图说明Description of drawings
图1为本发明制备流程图；Fig. 1 is the preparation flowchart of the present invention;
图2为本发明无电镀过程示意图；Fig. 2 is a schematic diagram of the electroless plating process of the present invention;
图3为实施例1在1mA下的放电曲线图；Fig. 3 is the discharge curve figure under 1mA of embodiment 1;
图4为实施例2制备流程图。Fig. 4 is the preparation flowchart of embodiment 2.
具体实施方式Detailed ways
下面结合附图及实施例，对本发明进行详细描述。The present invention will be described in detail below in conjunction with the accompanying drawings and embodiments.
参阅图1和图2，本发明包括：Referring to Fig. 1 and Fig. 2, the present invention comprises:
S1、用离子交换的方法在衬底11两端制备金属镍层12，具体包括：S1, prepare the metal nickel layer 12 at both ends of the substrate 11 by means of ion exchange, specifically comprising:
S1.1、用去离子水、乙醇及丙酮分别对衬底超声波清洗25～35 min，得到无尘化衬底11，烘干备用；S1.1. Use deionized water, ethanol and acetone to ultrasonically clean the substrate for 25-35 minutes respectively to obtain a dust-free substrate 11, and dry it for later use;
S1.2、将清洗烘干的衬底11两端分别置于硫酸镍溶液中浸泡10～15min，使得衬底表面进行金属离子吸附；S1.2. Soak both ends of the cleaned and dried substrate 11 in a nickel sulfate solution for 10-15 minutes, so that metal ions are adsorbed on the surface of the substrate;
S1.3、用去离子水冲洗烘干后，置于硼氢化钠溶液中浸泡3~5min，表面吸附离子与溶液发生反应，生成镍种子层21；S1.3. After rinsing and drying with deionized water, soak in sodium borohydride solution for 3 to 5 minutes, and the surface adsorbed ions react with the solution to form a nickel seed layer 21;
S1.4、用去离子水冲洗烘干后，接着放入商用无电镀镍溶液中浸泡20～30min，得到导电且致密的金属镍层12；S1.4. Rinse and dry with deionized water, then soak in a commercial electroless nickel plating solution for 20 to 30 minutes to obtain a conductive and dense metallic nickel layer 12;
S2、将S1所得的金属镍层12用去离子水冲洗烘干后，置于商用无电镀金溶液中浸泡20～30min，在镍层12表面制备金属金层13，得到镍/金电极，作为柔性纸基电池的集流体；S2. Rinse and dry the metallic nickel layer 12 obtained in S1 with deionized water, place it in a commercial electroless gold plating solution for 20-30 minutes, and prepare a metallic gold layer 13 on the surface of the nickel layer 12 to obtain a nickel/gold electrode as a current collector for a flexible paper-based battery;
S3、在S2所得的镍/金集流体的一端电镀银，将电沉积制得柔性银电极作为阴极14，具体包括：S3, electroplating silver on one end of the nickel/gold current collector obtained in S2, and making a flexible silver electrode by electrodeposition as the cathode 14, specifically including:
S3.1、配置镀银溶液；S3.1, configure the silver plating solution;
S3.2、待电镀的集流体作为阴极，银丝作为阳极，放入镀银溶液，在-0.5V电压下电镀10~20min；S3.2. The current collector to be electroplated is used as the cathode, and the silver wire is used as the anode, put into the silver plating solution, and electroplate at -0.5V for 10~20min;
S4、在S2所得的镍/金集流体另一端电镀锌，将电沉积制得柔性锌电极作为阳极15，具体包括：S4. Galvanizing the other end of the nickel/gold current collector obtained in S2, and making a flexible zinc electrode by electrodeposition as the anode 15, specifically including:
S4.1、配置镀锌溶液；S4.1, configure the galvanizing solution;
S4.2、待电镀的集流体作为工作电极，铂电极作为对电极，银-氯化银电极作为参比电极，在镀锌溶液中，加-0.8V电压，电镀10~20min；S4.2. The current collector to be electroplated is used as the working electrode, the platinum electrode is used as the counter electrode, and the silver-silver chloride electrode is used as the reference electrode. In the galvanizing solution, apply a voltage of -0.8V and electroplate for 10~20min;
S5、在S3、S4所得的阴极14、阳极15上引出导线16，滴上电解液17，得到柔性纸基电池。S5. Lead wires 16 from the cathode 14 and anode 15 obtained in S3 and S4, and drip the electrolyte 17 to obtain a flexible paper-based battery.
实施例1Example 1
S1、用离子交换的方法在衬底11两端制备金属镍层12，具体包括：S1, prepare the metal nickel layer 12 at both ends of the substrate 11 by means of ion exchange, specifically comprising:
S1.1、选取2cm*5cm的矩形滤纸作为衬底，用去离子水、乙醇及丙酮分别对衬底超声波清洗30 min，得到无尘化衬底11，烘干备用；S1.1. Select a rectangular filter paper of 2cm*5cm as the substrate, and ultrasonically clean the substrate with deionized water, ethanol and acetone for 30 minutes respectively to obtain a dust-free substrate 11, and dry it for later use;
S1.2、将清洗烘干的衬底11两端分别置于硫酸镍溶液中浸泡10min，使得衬底表面进行金属离子吸附；S1.2. Soak both ends of the cleaned and dried substrate 11 in a nickel sulfate solution for 10 minutes, so that metal ions are adsorbed on the surface of the substrate;
S1.3、用去离子水冲洗烘干后，置于硼氢化钠溶液中浸泡3min，表面吸附的离子与溶液发生反应，生成镍种子层；S1.3. After rinsing and drying with deionized water, soak in sodium borohydride solution for 3 minutes, and the ions adsorbed on the surface react with the solution to form a nickel seed layer;
S1.4、用去离子水冲洗烘干后，接着放入商用无电镀镍溶液中浸泡20min，获得导电且致密的金属镍层12；S1.4. Rinse and dry with deionized water, then soak in a commercial electroless nickel plating solution for 20 minutes to obtain a conductive and dense metallic nickel layer 12;
S2、将S1所得的金属镍层12用去离子水冲洗烘干后，置于商用无电镀金溶液中浸泡20min，在镍层12表面制备金属金层13，得到镍/金电极，作为柔性纸基电池的集流体；S2. Rinse and dry the metallic nickel layer 12 obtained in S1 with deionized water, place it in a commercial electroless gold plating solution and soak for 20 minutes, and prepare a metallic gold layer 13 on the surface of the nickel layer 12 to obtain a nickel/gold electrode as a current collector for a flexible paper-based battery;
S3、在S2所得的镍/金集流体的一端电镀银，将电沉积制得柔性银电极作为阴极14，具体包括：S3, electroplating silver on one end of the nickel/gold current collector obtained in S2, and making a flexible silver electrode by electrodeposition as the cathode 14, specifically including:
S3.1、将0.4M的硝酸银溶液和0.6M的硝酸钠溶液按1∶1的体积比混合，配置镀银溶液；S3.1, mix the silver nitrate solution of 0.4M and the sodium nitrate solution of 0.6M according to the volume ratio of 1:1, configure the silver plating solution;
S3.2、待电镀的集流体作为阴极，银丝作为阳极，放入镀银溶液，在-0.5V电压下电镀10min分钟；S3.2. The current collector to be electroplated is used as the cathode, and the silver wire is used as the anode, put into the silver plating solution, and electroplate at -0.5V for 10 minutes;
S4、在S2所得的镍/金集流体另一端电镀锌，将电沉积制得柔性锌电极作为阳极15，具体包括：S4. Galvanizing the other end of the nickel/gold current collector obtained in S2, and making a flexible zinc electrode by electrodeposition as the anode 15, specifically including:
S4.1、将0.6M的硫酸锌溶液和1M的柠檬酸三钠溶液按1∶1的体积比混合，配置镀锌溶液；S4.1. Mix 0.6M zinc sulfate solution and 1M trisodium citrate solution in a volume ratio of 1:1 to prepare a galvanizing solution;
S4.2、待电镀的集流体作为工作电极，铂电极作为对电极，银-氯化银电极作为参比电极，在镀锌溶液中，加-0.8V电压，电镀10min；S4.2. The current collector to be electroplated is used as the working electrode, the platinum electrode is used as the counter electrode, and the silver-silver chloride electrode is used as the reference electrode. In the galvanizing solution, apply a voltage of -0.8V and electroplate for 10 minutes;
S5、在S3、S4所得的阴极14、阳极15上引出导线16，滴上5M氯化钠溶液作为电解液17，得到柔性纸基电池。S5. Lead wires 16 from the cathode 14 and anode 15 obtained in S3 and S4, and drop 5M sodium chloride solution as electrolyte 17 to obtain a flexible paper-based battery.
制备的纸基电池开路电压为0.7V，短路电流约为4mA。图3为在1mA下的放电曲线，设置有效电压为大于0.3V，电压从0.65V下降到0.3V，用了230s。The prepared paper-based battery has an open circuit voltage of 0.7V and a short circuit current of about 4mA. Figure 3 is the discharge curve at 1mA, the effective voltage is set to be greater than 0.3V, and the voltage drops from 0.65V to 0.3V, and it takes 230s.
实施例2Example 2
纸基电池一般来说有两种结构，实施例1中展示的是平面型，还有一种堆叠结构，如图4。Generally speaking, paper-based batteries have two structures, the planar type shown in Example 1, and a stacked structure, as shown in Figure 4.
S1、用离子交换的方法在两个衬底11上制备金属镍层12，具体包括：S1, prepare metal nickel layer 12 on two substrates 11 with the method for ion exchange, specifically include:
S1.1、选取两张1cm*1cm的矩形硫酸纸作为衬底，用去离子水、乙醇及丙酮分别对衬底超声波清洗30 min，得到两个无尘化衬底11，烘干备用；S1.1. Select two pieces of 1cm*1cm rectangular sulfuric acid paper as substrates, and ultrasonically clean the substrates with deionized water, ethanol and acetone respectively for 30 minutes to obtain two dust-free substrates 11, and dry them for later use;
S1.2、将两个清洗烘干的衬底11分别置于硫酸镍溶液中浸泡15min，使得衬底表面进行金属离子吸附；S1.2. Soak the two cleaned and dried substrates 11 in a nickel sulfate solution for 15 minutes, so that metal ions are adsorbed on the surface of the substrates;
S1.3、用去离子水冲洗烘干后，置于硼氢化钠溶液中浸泡5min，表面吸附的离子与溶液发生反应，生成镍种子层；S1.3. After rinsing and drying with deionized water, soak in sodium borohydride solution for 5 minutes, and the ions adsorbed on the surface react with the solution to form a nickel seed layer;
S1.4、用去离子水冲洗烘干后，接着放入商用无电镀镍溶液中浸泡20min，获得两个导电且致密的金属镍层12；S1.4. Rinse and dry with deionized water, then soak in a commercial electroless nickel plating solution for 20 minutes to obtain two conductive and dense metallic nickel layers 12;
S2、将S1所得的两个金属镍层12用去离子水冲洗烘干后，分别置于商用无电镀金溶液中浸泡20min，在镍层12表面制备金属金层13，得到两个镍/金电极，作为柔性纸基电池的集流体；S2. Rinse and dry the two metallic nickel layers 12 obtained in S1 with deionized water, place them in a commercial electroless gold plating solution and soak them for 20 minutes, prepare a metallic gold layer 13 on the surface of the nickel layer 12, and obtain two nickel/gold electrodes as current collectors for flexible paper-based batteries;
S3、在S2所得的一个镍/金集流体上电镀银，将电沉积制得柔性银电极作为阴极14，具体包括：S3, electroplating silver on a nickel/gold current collector obtained in S2, and making a flexible silver electrode by electrodeposition as the cathode 14, specifically including:
S3.1、将0.4M的硝酸银溶液和0.6M的硝酸钠溶液按1∶1的体积比混合，配置镀银溶液；S3.1, mix the silver nitrate solution of 0.4M and the sodium nitrate solution of 0.6M according to the volume ratio of 1:1, configure the silver plating solution;
S3.2、待电镀的集流体作为阴极，银丝作为阳极，放入镀银溶液，在-0.5V电压下电镀20min；S3.2. The current collector to be electroplated is used as the cathode, and the silver wire is used as the anode, put into the silver plating solution, and electroplate at -0.5V for 20 minutes;
S4、在S2所得的另一个镍/金集流体上电镀锌，将电沉积制得柔性锌电极作为阳极15，具体包括：S4, electroplate zinc on another nickel/gold current collector obtained in S2, and make a flexible zinc electrode by electrodeposition as the anode 15, specifically including:
S4.1、将0.6M的硫酸锌溶液和1M的柠檬酸三钠溶液按1∶1的体积比混合，配置镀锌溶液；S4.1. Mix 0.6M zinc sulfate solution and 1M trisodium citrate solution in a volume ratio of 1:1 to prepare a galvanizing solution;
S4.2、待电镀的集流体作为工作电极，铂电极作为对电极，银-氯化银电极作为参比电极，在镀锌溶液中，加-0.8V电压，电镀20min；S4.2. The current collector to be electroplated is used as the working electrode, the platinum electrode is used as the counter electrode, and the silver-silver chloride electrode is used as the reference electrode. In the galvanizing solution, apply a voltage of -0.8V and electroplate for 20 minutes;
S5、在S3、S4所得的阴极14、阳极15上引出导线16，在阴极14、阳极15中间用一张硫酸纸11隔离，堆叠起来，封装后，在所得器件中央滴上2M氯化钠溶液作为电解液17，得到堆叠结构的柔性纸基电池。S5. Lead wires 16 on the cathode 14 and anode 15 obtained in S3 and S4, isolate the cathode 14 and anode 15 with a piece of sulfuric acid paper 11, stack them up, and after packaging, drop 2M sodium chloride solution in the center of the obtained device as the electrolyte 17 to obtain a flexible paper-based battery with a stacked structure.
本发明工作原理是这样的：The working principle of the present invention is as follows:
参阅图1，本发明制备方法包括，首先在滤纸上通过离子交换法实现滤纸上长金属镍，镍和纸基衬底结合力强、柔性大、还具有良好的导电能力。然后在镍层表面无电镀一层金纳米粒子，可以提高通过无电镀沉积制得的镍层的化学稳定性，减少磷等杂质的干扰，并且进一步提高了镍电极的电导率，以镍/金电极作为柔性纸基电池的集流体。然后，用电镀的方法分别在镍电极上沉积银和锌。最后，进行简单的封装，滴上电解液便实现了纸基电池的制备。本发明所制备的纸基电池属于银锌电池，具有柔性、轻便、低成本、制作过程绿色无毒的优点。Referring to Fig. 1, the preparation method of the present invention includes, firstly, metal nickel is grown on the filter paper by the ion exchange method on the filter paper, and the nickel and the paper-based substrate have strong bonding force, great flexibility, and good electrical conductivity. Then electroless plating a layer of gold nanoparticles on the surface of the nickel layer can improve the chemical stability of the nickel layer deposited by electroless plating, reduce the interference of impurities such as phosphorus, and further improve the conductivity of the nickel electrode. The nickel/gold electrode is used as the current collector of the flexible paper-based battery. Then, silver and zinc were respectively deposited on the nickel electrodes by electroplating. Finally, simple packaging is carried out, and the electrolyte is dripped to realize the preparation of paper-based batteries. The paper-based battery prepared by the invention belongs to the silver-zinc battery and has the advantages of flexibility, lightness, low cost, green and non-toxic manufacturing process.
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