CN114388902B - Method for inhibiting zinc dendrite growth in zinc ion battery - Google Patents
Method for inhibiting zinc dendrite growth in zinc ion battery Download PDFInfo
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000011701 zinc Substances 0.000 title claims abstract description 51
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 51
- 210000001787 dendrite Anatomy 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 15
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims description 20
- 230000002401 inhibitory effect Effects 0.000 title claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920002907 Guar gum Polymers 0.000 claims abstract description 16
- 239000000665 guar gum Substances 0.000 claims abstract description 16
- 229960002154 guar gum Drugs 0.000 claims abstract description 16
- 235000010417 guar gum Nutrition 0.000 claims abstract description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 239000000084 colloidal system Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 230000003044 adaptive effect Effects 0.000 claims description 10
- 239000007784 solid electrolyte Substances 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 6
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229960003351 prussian blue Drugs 0.000 claims description 3
- 239000013225 prussian blue Substances 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- -1 borate ester Chemical class 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 150000002314 glycerols Chemical class 0.000 claims description 2
- 230000001632 homeopathic effect Effects 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 26
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000011056 performance test Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 239000011245 gel electrolyte Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 239000000017 hydrogel Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Classifications
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- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
技术领域Technical field
本发明属于材料化学技术领域,具体涉及一种抑制锌离子电池中锌枝晶生长的方法。The invention belongs to the technical field of material chemistry, and specifically relates to a method for inhibiting the growth of zinc dendrites in zinc ion batteries.
背景技术Background technique
当今社会的快速发展刺激了对于柔性和可穿戴设备的需求,主要包括便携式电子产品和智能可穿戴系统。在过去的几年里,人们致力于制造高性能的柔性锂离子电池。然而,尽管锂离子电池提供了较高的能量和功率密度,但安全问题和锂金属资源的限制使其实际应用面临巨大障碍。事实上,安全和无毒是可穿戴储能设备至关重要的前提条件。在这种情况下,一种替代策略,锌离子电池由于其固有的安全性、易于制造、且具有低的成本等性能引起了极大的关注。然而,水系锌离子电池长期以来受到严重的锌枝晶影响以及水系电解液中的副反应,最终会增加界面阻抗,引起电池短路等一系列问题,从而影响锌基电池的循环性能和使用寿命等性能。The rapid development of today's society has stimulated the demand for flexible and wearable devices, mainly including portable electronic products and smart wearable systems. Over the past few years, efforts have been devoted to creating high-performance, flexible lithium-ion batteries. However, although lithium-ion batteries provide high energy and power density, safety issues and limitations of lithium metal resources make their practical applications face huge obstacles. In fact, safety and non-toxicity are crucial prerequisites for wearable energy storage devices. In this context, an alternative strategy, zinc-ion batteries, has attracted great attention due to its inherent safety, ease of fabrication, and low cost. However, aqueous zinc-ion batteries have long been severely affected by zinc dendrites and side reactions in the aqueous electrolyte, which will eventually increase the interface impedance and cause a series of problems such as battery short circuit, thereby affecting the cycle performance and service life of zinc-based batteries. performance.
科研工作者通过构筑三维聚合物电解质,包括抗老化凝胶,离子限域凝胶以及人工界面层,并被证明可有效抑制电解质与锌负极之间的界面副反应。然而,在准固态电池构筑中,固-固界面接触是急需攻克的难题。1)在充放电过程中,枝晶的动态生长与溶解,使得静态的电解质界面与动态的锌负极界面之间不能保持紧密的连接,出现微空隙,从而导致界面接触不良,降低电池的倍率能力。2)大多数水凝胶在干燥条件下往往会严重失水,这对于水凝胶的实际应用来说是一个致命的缺陷。因此,构建动态且强大的界面接触以及具有可靠的保水能力的水凝胶至关重要,这是高效准固态锌离子电池界面策略的关键原则。Researchers constructed three-dimensional polymer electrolytes, including anti-aging gels, ion-confined gels and artificial interface layers, and were proven to effectively suppress interfacial side reactions between electrolytes and zinc anodes. However, in the construction of quasi-solid-state batteries, solid-solid interface contact is an urgent problem that needs to be overcome. 1) During the charge and discharge process, the dynamic growth and dissolution of dendrites prevents the static electrolyte interface and the dynamic zinc anode interface from maintaining a tight connection, resulting in micro-gaps, resulting in poor interface contact and reducing the rate capability of the battery. . 2) Most hydrogels tend to severely lose water under dry conditions, which is a fatal flaw for practical applications of hydrogels. Therefore, it is crucial to construct hydrogels with dynamic and strong interfacial contacts as well as reliable water retention capabilities, which are key principles for interfacial strategies for efficient quasi-solid-state zinc-ion batteries.
在此,通过对天然高分子进行交联,再通过引入第二层网络结构,最终得到了具有超快自修复和优异的保水性能的水凝胶。Here, by cross-linking natural polymers and introducing a second layer of network structure, a hydrogel with ultra-fast self-healing and excellent water retention properties was finally obtained.
发明内容Contents of the invention
本发明的目的在于解决准固态锌离子电池中不连续的固-固界面问题及其引发的严重的锌枝晶生长,提出一种抑制锌离子电池中锌枝晶生长的方法。The purpose of the present invention is to solve the problem of discontinuous solid-solid interface in quasi-solid zinc ion batteries and the severe zinc dendrite growth caused by it, and to propose a method for inhibiting the growth of zinc dendrites in zinc ion batteries.
为了实现上述目的,本发明的技术方案是:一种抑制锌离子电池中锌枝晶生长的方法,其特征在于包括如下步骤:In order to achieve the above objects, the technical solution of the present invention is: a method for inhibiting the growth of zinc dendrites in zinc ion batteries, which is characterized by comprising the following steps:
1)将一定量的瓜尔胶完全溶解到锌盐溶液中,形成均匀的胶体;1) Completely dissolve a certain amount of guar gum into the zinc salt solution to form a uniform colloid;
2)将适量的甘油添加到上述制备的胶体中以形成二元溶剂系统;2) Add an appropriate amount of glycerol to the colloid prepared above to form a binary solvent system;
3)加入中性有机硼交联剂并使其固化,获得自修复和自适应的准固态电解质;3) Add a neutral organic boron cross-linking agent and solidify it to obtain a self-healing and adaptive quasi-solid electrolyte;
4)将锌阳极、阴极材料和自适应的准固态电解质组装成无枝晶生长的准固态锌离子电池。4) Assemble zinc anode, cathode materials and adaptive quasi-solid-state electrolyte into a quasi-solid-state zinc-ion battery without dendrite growth.
按上述方案,步骤1)中瓜尔胶与锌盐溶液的质量比为1%-6%。According to the above scheme, the mass ratio of guar gum and zinc salt solution in step 1) is 1%-6%.
按上述方案,步骤1)中锌盐溶液为硫酸锌,三氟甲烷磺酸锌和氯化锌中的任意一种。According to the above scheme, the zinc salt solution in step 1) is any one of zinc sulfate, zinc trifluoromethanesulfonate and zinc chloride.
按上述方案,步骤2)中甘油:锌盐溶液体积比为0.15%-2%。According to the above scheme, the volume ratio of glycerol:zinc salt solution in step 2) is 0.15%-2%.
按上述方案,步骤4)中阴极材料为聚吡咯、聚苯胺、钒氧化物、普鲁士蓝和锰氧化物中的任意一种。According to the above scheme, the cathode material in step 4) is any one of polypyrrole, polyaniline, vanadium oxide, Prussian blue and manganese oxide.
本发明制备得到一种具有超快自修复性能的电解质,动态适应锌负极的收缩与膨胀,构筑自适应界面,抑制锌枝晶的生长,在一定的电流密度下情况下,进行对称电池的充放电循环实验,750次循环后,锌表面沉积均匀,无枝晶生长,且电解质与负极界面保持紧密的连接。The invention prepares an electrolyte with ultra-fast self-healing performance, which dynamically adapts to the shrinkage and expansion of the zinc negative electrode, builds an adaptive interface, inhibits the growth of zinc dendrites, and performs symmetrical battery charging at a certain current density. In the discharge cycle experiment, after 750 cycles, the zinc surface was deposited evenly, without dendrite growth, and the interface between the electrolyte and the negative electrode remained tightly connected.
本发明的有益效果是:本发明利用有机硼交联剂与瓜尔胶中的顺势二醇之间形成的动态硼酸酯,构筑了一个具有超快自修复性能的电解质。该电解质具有高保水性,而且可以动态的适应锌负极的膨胀与收缩,使得电解质/电极界面始终保持连续且紧密的接触状态,抑制锌负极枝晶的生长。其中,甘油可以与水分子形成大量的分子间氢键,抑制水分子的蒸发,从而增强凝胶的锁水能力。此外,甘油-水二元体系通过在聚合物网络中引入非共价键,大大增强了凝胶的机械韧性。The beneficial effects of the present invention are: the present invention utilizes the dynamic borate ester formed between the organic boron cross-linking agent and the homeopathic diol in guar gum to construct an electrolyte with ultra-fast self-healing performance. The electrolyte has high water retention and can dynamically adapt to the expansion and contraction of the zinc anode, so that the electrolyte/electrode interface always maintains continuous and close contact and inhibits the growth of zinc anode dendrites. Among them, glycerol can form a large number of intermolecular hydrogen bonds with water molecules, inhibiting the evaporation of water molecules, thereby enhancing the gel's water-locking ability. In addition, the glycerol-water binary system greatly enhances the mechanical toughness of the gel by introducing non-covalent bonds into the polymer network.
本发明具有原料廉价可降解、工艺简单环保、材料电化学性能优异的特点,并具有大规模应用的潜力。The invention has the characteristics of cheap and degradable raw materials, simple and environmentally friendly process, excellent electrochemical properties of the material, and has the potential for large-scale application.
附图说明Description of the drawings
图1是实施例1制备的自修复电解质的SEM图;Figure 1 is an SEM image of the self-healing electrolyte prepared in Example 1;
图2是实施例1制备的自修复电解质的FTIR图;Figure 2 is an FTIR pattern of the self-healing electrolyte prepared in Example 1;
图3是实施例1制备的自修复电解质的保水性能测试图;Figure 3 is a water retention performance test chart of the self-healing electrolyte prepared in Example 1;
图4是实施例1制备的自修复电解质的自修复性能宏观表征;Figure 4 is a macroscopic representation of the self-healing performance of the self-healing electrolyte prepared in Example 1;
图5是实施例1制备的自修复电解质的原位自修复性能光学图;Figure 5 is an optical diagram of the in-situ self-healing performance of the self-healing electrolyte prepared in Example 1;
图6是使用本发明所得到的自修复电解质和普通瓜尔胶电解质分别用作锌//锌对称电池中的电解质,在电流密度为0.5mA cm-2的情况下,锌//锌对称电池的充放电循环图。Figure 6 shows the self-healing electrolyte and ordinary guar gum electrolyte obtained by using the present invention as electrolytes in a zinc//zinc symmetrical battery respectively. When the current density is 0.5mA cm -2 , the zinc//zinc symmetrical battery The charge and discharge cycle diagram.
具体实施方式Detailed ways
为了更好地理解本发明,下面结合实施例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。In order to better understand the present invention, the content of the present invention will be further explained below in conjunction with the examples, but the content of the present invention is not limited only to the following examples.
实施例1:Example 1:
1)将0.4g瓜尔胶溶解到10mL的1.5M三氟甲烷磺酸锌溶液中。1) Dissolve 0.4g guar gum into 10mL of 1.5M zinc trifluoromethanesulfonate solution.
2)上述溶液完全溶解后加入0.1ml丙三醇磁力搅拌30min。2) After the above solution is completely dissolved, add 0.1 ml glycerol and stir magnetically for 30 minutes.
3)将1ml中性有机硼交联剂逐滴缓慢的加入到上述混合溶液中,并用玻璃棒搅拌,获得具有自修复和自适应的准固态电解质。3) Slowly add 1 ml of neutral organic boron cross-linking agent into the above mixed solution drop by drop, and stir with a glass rod to obtain a self-healing and adaptive quasi-solid electrolyte.
4)将锌阳极、锰氧化物阴极和凝胶电解质组装成无枝晶生长的准固态锌离子电池。4) Assemble the zinc anode, manganese oxide cathode and gel electrolyte into a quasi-solid zinc-ion battery without dendrite growth.
以本实施例所得到的瓜尔胶电解质为多孔网络结构(图1),FTIR图能谱显示出生成了动态B-O键(图2),且该凝胶电解质具有优异的保水性能(图3)和超快的自修复性能(图4和图5)。从图3中可以看出,纯瓜尔胶水凝胶的锁水能力最低,失水重量为3克,比初始质量减少了70%。相比之下,本发明制备得到的自修复电解质的锁水容量在前2天内缓慢上升至102%,这可以归因于瓜尔胶分子的吸湿性。此后,尽管波动,但保持稳定,并在接下来的6天内保持在100%左右。图4从宏观上证明了凝胶的自修复性能,图5从微观上证明了凝胶的自修复性能,可以在30秒内实现自愈合。锌电池中不使用本发明中的自修复电解质时,在电流密度为1mA cm-2的情况下,电池的充放电循环550h后,电压急剧变大;当锌电池中使用本发明中的自修复电解质时,在电流密度为1mA cm-2的情况下,电池充放电循环1500h其电压平稳(图6),表明锌在电极沉积均匀,锌枝晶生长得到抑制,延长了锌电极的使用寿命。The guar gum electrolyte obtained in this example has a porous network structure (Figure 1), and the FTIR energy spectrum shows the formation of dynamic BO bonds (Figure 2), and the gel electrolyte has excellent water retention properties (Figure 3) and ultra-fast self-healing performance (Figures 4 and 5). As can be seen from Figure 3, pure guar gum hydrogel has the lowest water-locking ability, and the water loss weight is 3 grams, which is 70% less than the initial mass. In contrast, the water-locking capacity of the self-healing electrolyte prepared by the present invention slowly increased to 102% within the first 2 days, which can be attributed to the hygroscopicity of guar gum molecules. After that, despite the fluctuations, it remained stable and stayed around 100% for the next 6 days. Figure 4 proves the self-healing properties of the gel from a macro perspective, and Figure 5 demonstrates the self-healing properties of the gel from a micro perspective, and can achieve self-healing within 30 seconds. When the self-repairing electrolyte of the present invention is not used in a zinc battery, when the current density is 1 mA cm -2 , the voltage of the battery increases sharply after 550 hours of charge and discharge cycles; when the self-repairing electrolyte of the present invention is used in a zinc battery In the case of electrolyte, when the current density is 1mA cm -2 , the voltage of the battery is stable after 1500h of charge and discharge cycles (Figure 6), indicating that zinc is uniformly deposited on the electrode, the growth of zinc dendrites is inhibited, and the service life of the zinc electrode is extended.
实施例2:Example 2:
1)将0.4g瓜尔胶溶解到10mL的1.5M三氟甲烷磺酸锌溶液中。1) Dissolve 0.4g guar gum into 10mL of 1.5M zinc trifluoromethanesulfonate solution.
2)上述溶液完全溶解后加入0.2ml丙三醇磁力搅拌30min。2) After the above solution is completely dissolved, add 0.2 ml of glycerol and stir magnetically for 30 minutes.
3)将1ml中性有机硼交联剂逐滴缓慢的加入到上述混合溶液中,并用玻璃棒搅拌,获得具有自修复和自适应的准固态电解质。3) Slowly add 1 ml of neutral organic boron cross-linking agent into the above mixed solution drop by drop, and stir with a glass rod to obtain a self-healing and adaptive quasi-solid electrolyte.
4)将锌阳极、聚苯胺阴极和凝胶电解质组装成无枝晶生长的准固态锌离子电池。4) Assemble the zinc anode, polyaniline cathode and gel electrolyte into a quasi-solid zinc-ion battery without dendrite growth.
将上述所制备的材料进行SEM,FTIR,保水性能测试分析以及电化学性能测试。在8天的测试周期内,保水性能保持稳定。电化学性能测试中显示均匀的锌沉积,锌枝晶生长得到抑制,延长了锌电极的使用寿命。The materials prepared above were subjected to SEM, FTIR, water retention performance test analysis and electrochemical performance test. The water retention performance remained stable during the 8-day test period. The electrochemical performance test showed uniform zinc deposition, inhibited zinc dendrite growth, and extended the service life of the zinc electrode.
实施例3:Example 3:
1)将0.4g瓜尔胶溶解到10mL的1.5M三氟甲烷磺酸锌溶液中。1) Dissolve 0.4g guar gum into 10mL of 1.5M zinc trifluoromethanesulfonate solution.
2)上述溶液完全溶解后加入0.1ml丙三醇磁力搅拌30min。2) After the above solution is completely dissolved, add 0.1 ml glycerol and stir magnetically for 30 minutes.
3)将2ml中性有机硼交联剂逐滴缓慢的加入到上述混合溶液中,并用玻璃棒搅拌,获得具有自修复和自适应的准固态电解质。3) Slowly add 2 ml of neutral organic boron cross-linking agent into the above mixed solution drop by drop, and stir with a glass rod to obtain a self-healing and adaptive quasi-solid electrolyte.
4)将锌阳极、聚吡咯阴极和凝胶电解质组装成无枝晶生长的准固态锌离子电池。4) Assemble the zinc anode, polypyrrole cathode and gel electrolyte into a quasi-solid zinc-ion battery without dendrite growth.
将上述所制备的材料进行SEM,FTIR,保水性能测试分析以及电化学性能测试。在8天的测试周期内,保水性能保持稳定。电化学性能测试中显示均匀的锌沉积,锌枝晶生长得到抑制,延长了锌电极的使用寿命。The materials prepared above were subjected to SEM, FTIR, water retention performance test analysis and electrochemical performance test. The water retention performance remained stable during the 8-day test period. The electrochemical performance test showed uniform zinc deposition, inhibited zinc dendrite growth, and extended the service life of the zinc electrode.
实施例4:Example 4:
1)将0.6g瓜尔胶溶解到10mL的1.5M三氟甲烷磺酸锌溶液中。1) Dissolve 0.6g guar gum into 10mL of 1.5M zinc trifluoromethanesulfonate solution.
2)上述溶液完全溶解后加入0.1ml丙三醇磁力搅拌30min。2) After the above solution is completely dissolved, add 0.1 ml glycerol and stir magnetically for 30 minutes.
3)将1ml中性有机硼交联剂逐滴缓慢的加入到上述混合溶液中,并用玻璃棒搅拌,获得具有自修复和自适应的准固态电解质。3) Slowly add 1 ml of neutral organic boron cross-linking agent into the above mixed solution drop by drop, and stir with a glass rod to obtain a self-healing and adaptive quasi-solid electrolyte.
4)将锌阳极、钒氧化物阴极和凝胶电解质组装成无枝晶生长的准固态锌离子电池。4) Assemble the zinc anode, vanadium oxide cathode and gel electrolyte into a quasi-solid zinc-ion battery without dendrite growth.
将上述所制备的材料进行SEM、FTIR、力学性能测试分析以及电化学性能测试。在8天的测试周期内,保水性能保持稳定。电化学性能测试中显示均匀的锌沉积,锌枝晶生长得到抑制,延长了锌电极的使用寿命。The materials prepared above were subjected to SEM, FTIR, mechanical property test analysis and electrochemical property test. The water retention performance remained stable during the 8-day test period. The electrochemical performance test showed uniform zinc deposition, inhibited zinc dendrite growth, and extended the service life of the zinc electrode.
实施例5:Example 5:
1)将0.6g瓜尔胶溶解到10mL的1.5M氯化锌溶液中。1) Dissolve 0.6g guar gum into 10mL of 1.5M zinc chloride solution.
2)上述溶液完全溶解后加入0.1ml丙三醇磁力搅拌30min。2) After the above solution is completely dissolved, add 0.1 ml glycerol and stir magnetically for 30 minutes.
3)将1ml中性有机硼交联剂逐滴缓慢的加入到上述混合溶液中,并用玻璃棒搅拌,获得具有自修复和自适应的准固态电解质。3) Slowly add 1 ml of neutral organic boron cross-linking agent into the above mixed solution drop by drop, and stir with a glass rod to obtain a self-healing and adaptive quasi-solid electrolyte.
4)将锌阳极、普鲁士蓝阴极和凝胶电解质组装成无枝晶生长的准固态锌离子电池。4) Assemble the zinc anode, Prussian blue cathode and gel electrolyte into a quasi-solid zinc-ion battery without dendrite growth.
将上述所制备的材料进行SEM、FTIR、力学性能测试分析以及电化学性能测试。在8天的测试周期内,保水性能保持稳定。电化学性能测试中显示均匀的锌沉积,锌枝晶生长得到抑制,延长了锌电极的使用寿命。The materials prepared above were subjected to SEM, FTIR, mechanical property test analysis and electrochemical property test. The water retention performance remained stable during the 8-day test period. The electrochemical performance test showed uniform zinc deposition, inhibited zinc dendrite growth, and extended the service life of the zinc electrode.
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CN109411833A (en) * | 2018-10-26 | 2019-03-01 | 北京大学深圳研究生院 | A kind of solid electrolyte, its preparation method and application |
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CN109411833A (en) * | 2018-10-26 | 2019-03-01 | 北京大学深圳研究生院 | A kind of solid electrolyte, its preparation method and application |
WO2020217782A1 (en) * | 2019-04-25 | 2020-10-29 | 三洋化成工業株式会社 | Negative electrode addditive for alkaline battery, and alkaline battery |
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