CN106450488B - A kind of in-situ preparation method of lithium-sulfur battery based on silicon negative electrode - Google Patents
A kind of in-situ preparation method of lithium-sulfur battery based on silicon negative electrode Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 74
- 239000010703 silicon Substances 0.000 title claims abstract description 74
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 130
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 120
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052802 copper Inorganic materials 0.000 claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000003860 storage Methods 0.000 claims abstract description 20
- 238000003475 lamination Methods 0.000 claims abstract description 11
- 239000011889 copper foil Substances 0.000 claims description 23
- 239000011888 foil Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- -1 copper metal compound Chemical class 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 claims 1
- 239000002905 metal composite material Substances 0.000 abstract description 30
- 230000008569 process Effects 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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Abstract
本发明公开一种基于硅负极的锂硫电池的原位制备方法。本发明通过按照锂硫电池正极极片、锂/铜金属复合电极片、硅电极片和锂/铜金属复合电极片的叠片顺序制备三电极锂硫叠片电池后，使用原位预储锂的方法对硅电极片进行预储锂，预储锂结束后，将锂/铜金属复合电极片取出并原位封装，得到以硅电极片为负极的锂硫电池。该方法简化了硅基锂硫电池的制备工艺流程，省去拆电池、取极片及重复制片的流程，规避了现有工艺的失效风险，易转化为工业生产技术。
The invention discloses an in-situ preparation method of a lithium-sulfur battery based on a silicon negative electrode. In the present invention, after preparing a three-electrode lithium-sulfur laminated battery according to the lamination sequence of the lithium-sulfur battery positive electrode sheet, lithium/copper metal composite electrode sheet, silicon electrode sheet, and lithium/copper metal composite electrode sheet, the in-situ pre-stored lithium According to the method, lithium is pre-stored on the silicon electrode sheet. After the lithium pre-storage is completed, the lithium/copper metal composite electrode sheet is taken out and packaged in situ to obtain a lithium-sulfur battery with the silicon electrode sheet as the negative electrode. The method simplifies the preparation process of the silicon-based lithium-sulfur battery, saves the process of dismantling the battery, taking the pole piece and repeating the film, avoids the failure risk of the existing process, and is easy to transform into an industrial production technology.
Description
技术领域technical field
本发明属于锂硫电池技术领域，涉及一种基于硅负极的锂硫电池的原位制备方法。The invention belongs to the technical field of lithium-sulfur batteries, and relates to an in-situ preparation method of a lithium-sulfur battery based on a silicon negative electrode.
背景技术Background technique
锂硫电池是一种高能量密度的二次化学电源，随着消费类电子产品、新能源汽车及储能系统等领域的快速发展，锂硫电池备受关注。硫正极的比容量高达1675mAh/g，远远高于商业上广泛应用的钴酸锂电池的材料。金属锂的理论比容量为3860mAh/g，锂硫电池理论能量密度高达2600Wh/kg，并且硫是一种对环境友好的元素，对环境基本没有污染，考虑到硫的成本较低，所以，锂硫电池在下一代动力电池中有非常好的应用前景。Lithium-sulfur battery is a secondary chemical power source with high energy density. With the rapid development of consumer electronics, new energy vehicles and energy storage systems, lithium-sulfur batteries have attracted much attention. The specific capacity of the sulfur cathode is as high as 1675mAh/g, which is much higher than that of lithium cobalt oxide batteries, which are widely used commercially. The theoretical specific capacity of lithium metal is 3860mAh/g, and the theoretical energy density of lithium-sulfur batteries is as high as 2600Wh/kg. Sulfur is an environmentally friendly element that basically does not pollute the environment. Considering the low cost of sulfur, lithium Sulfur batteries have very good application prospects in the next generation of power batteries.
锂硫电池使用具有硫-硫键的硫基化合物作为正极活性物质，锂的多硫化合物溶于电解液，与高活性的锂金属负极发生反应，易造成穿梭效应，导致活性物质损失，造成自放电，影响循环性能。Lithium-sulfur batteries use sulfur-based compounds with sulfur-sulfur bonds as the positive electrode active material. Lithium polysulfide compounds dissolve in the electrolyte and react with the highly active lithium metal negative electrode, which is likely to cause a shuttle effect, resulting in the loss of active materials and resulting in self-destruction. discharge, affecting cycle performance.
锂硫电池一般采用金属锂箔做负极，金属锂具有较高的化学反应活性，化学不稳定，与硫基化合物副反应较多，产生自放电；而且，锂的熔点低，电池失效情况下，易与电解质、水分、空气剧烈反应，产生爆炸；另外，锂负极在循环过程中，易产生死区、锂枝晶，影响电池循环性能，甚至锂枝晶会刺穿隔膜，导致内部短路。Lithium-sulfur batteries generally use metal lithium foil as the negative electrode. Metal lithium has high chemical reactivity, is chemically unstable, and has many side reactions with sulfur-based compounds, resulting in self-discharge; moreover, the melting point of lithium is low. It is easy to react violently with electrolyte, moisture, and air, resulting in explosion; in addition, during the cycle of lithium negative electrode, it is easy to generate dead zone and lithium dendrites, which affect the battery cycle performance, and even lithium dendrites will pierce the separator, resulting in internal short circuit.
为避免使用金属锂负极带来的锂硫电池负面的作用，非锂金属负极得到了广泛的关注和研究。专利CN101465441公开了一种以石墨为负极的锂硫电池及该电池的制备方法，其通过电化学嵌锂的方法，预先在硫正极中补充锂源(预储锂)，负极采用无锂源的结构稳定的石墨负极，替代了高活性的金属锂，提高了锂硫电池的安全性和循环稳定性。专利CN102694158A公开了一种以过量沉积锂的含硅锂负极的锂硫电池的制备方法，该负极可降低锂枝晶的形成概率，改善电池循环性能和安全性能。In order to avoid the negative effects of lithium-sulfur batteries caused by the use of metal lithium anodes, non-lithium metal anodes have received extensive attention and research. Patent CN101465441 discloses a lithium-sulfur battery with graphite as the negative electrode and the preparation method of the battery. It uses the method of electrochemical lithium intercalation to supplement the lithium source (pre-storage lithium) in the sulfur positive electrode in advance, and the negative electrode adopts a lithium-free battery. The structurally stable graphite anode replaces the highly active metal lithium, which improves the safety and cycle stability of lithium-sulfur batteries. Patent CN102694158A discloses a preparation method of a lithium-sulfur battery with a silicon-containing lithium negative electrode deposited in excess of lithium. The negative electrode can reduce the formation probability of lithium dendrites and improve battery cycle performance and safety performance.
含硅负极具有比锂负极高的理论容量，硅负极的理论容量为4198mAh/g，氧化亚硅的理论容量为1964mAh/g，采用含硅负极替代金属锂负极制备锂硫电池，可以克服金属锂的高的化学不稳定性及锂枝晶的产生，并且可以提升锂硫电池的安全性和循环稳定性。但是，该类非锂金属电池的制备，需要首先制备预储锂电极，然后拆开电池，取出预储锂极片，然后再制片，组装成锂硫电池，该类电池制备方法较复杂，制备过程中失效风险大，且制备步骤繁琐条件苛刻不利于工业生产，或多或少的限制了大规模应用。The silicon-containing negative electrode has a higher theoretical capacity than the lithium negative electrode. The theoretical capacity of the silicon negative electrode is 4198mAh/g, and the theoretical capacity of the silicon oxide is 1964mAh/g. The silicon-containing negative electrode is used to replace the metal lithium negative electrode to prepare a lithium-sulfur battery, which can overcome the metal lithium. The high chemical instability and the generation of lithium dendrites can improve the safety and cycle stability of lithium-sulfur batteries. However, the preparation of this type of non-lithium metal battery requires the preparation of a pre-stored lithium electrode first, then disassemble the battery, take out the pre-stored lithium pole piece, and then make the piece and assemble it into a lithium-sulfur battery. The preparation method of this type of battery is relatively complicated. The risk of failure in the preparation process is high, and the preparation steps are cumbersome and harsh conditions are not conducive to industrial production, which more or less limits large-scale application.
发明内容Contents of the invention
本发明目的是提供一种基于硅负极的锂硫电池的原位制备方法，该制备方法可控性高，简化了硅基锂硫电池的制备工艺流程，规避了现有工艺的失效风险，易转化为工业生产技术。The purpose of the present invention is to provide an in-situ preparation method of a lithium-sulfur battery based on a silicon negative electrode. Transformed into industrial production technology.
本发明是这样实现的，一种基于硅负极的锂硫电池的原位制备方法，包括步骤：The present invention is achieved in this way, an in-situ preparation method of a lithium-sulfur battery based on a silicon negative electrode, comprising steps:
第一步：制备锂/铜金属复合电极片，该极片包括铜箔以及贴附于铜箔之上作为锂源的金属锂形成的锂箔；The first step: preparing a lithium/copper metal composite electrode sheet, the electrode sheet includes a copper foil and a lithium foil formed by metallic lithium attached to the copper foil as a lithium source;
第二步：按照锂硫电池正极极片、锂/铜金属复合电极片、含硅电极片和锂/铜金属复合电极片的叠片顺序进行叠片，制备三电极锂硫叠片电池；Step 2: Laminate according to the lamination sequence of the lithium-sulfur battery positive electrode sheet, lithium/copper metal composite electrode sheet, silicon-containing electrode sheet, and lithium/copper metal composite electrode sheet to prepare a three-electrode lithium-sulfur laminated battery;
第三步：使用原位电化学预储锂的方法对含硅电极片进行预储锂；Step 3: Pre-store lithium on the silicon-containing electrode sheet by using the method of in-situ electrochemical pre-storage of lithium;
第四步：预储锂结束后，在气体保护环境下将锂/铜金属复合电极片取出，然后对极组除气并进行直封，得到以含硅电极片为负极的两电极锂硫电池。Step 4: After the pre-storage of lithium is completed, the lithium/copper metal composite electrode sheet is taken out in a gas-protected environment, and then the electrode group is degassed and directly sealed to obtain a two-electrode lithium-sulfur battery with a silicon-containing electrode sheet as the negative electrode .
所述锂/铜金属复合电极片中，所述铜箔作为金属锂的结构支撑、集流体和极耳使用；或作为极耳使用。In the lithium/copper metal composite electrode sheet, the copper foil is used as a structural support, a current collector and a tab for lithium metal; or used as a tab.
所述铜箔作为金属锂的结构支撑、集流体和极耳使用时，锂箔/含硅电极片的容量比为1-10；所述铜箔作为极耳使用时，锂箔/含硅电极片的容量比为2-10。When the copper foil is used as a structural support, current collector and tab of metal lithium, the capacity ratio of lithium foil/silicon-containing electrode sheet is 1-10; when the copper foil is used as a tab, the lithium foil/silicon-containing electrode The capacity ratio of the sheet is 2-10.
所述锂箔的厚度为10-200微米，铜箔的厚度为5-20微米。The thickness of the lithium foil is 10-200 microns, and the thickness of the copper foil is 5-20 microns.
所述含硅电极片包括活性物质为硅单质的硅电极片和活性物质为氧化亚硅的氧化亚硅电极片。The silicon-containing electrode sheet includes a silicon electrode sheet whose active material is simple silicon and a silicon oxide electrode sheet whose active material is silicon oxide.
第二步中，电极叠片时，锂硫电池正极极片和含硅电极片的极耳在电池同一侧，作为电池的首侧；锂/铜电极片的极耳在首侧相对的一侧，作为电池的尾侧。In the second step, when the electrodes are stacked, the tabs of the positive pole piece of the lithium-sulfur battery and the silicon-containing electrode piece are on the same side of the battery as the first side of the battery; the tabs of the lithium/copper electrode piece are on the opposite side of the first side , as the tail side of the battery.
第三步中，对含硅电极片进行预储锂是以含硅电极片为正极，以锂/铜金属复合电极片为负极，采用原位电化学方法预储锂。In the third step, lithium is pre-stored on the silicon-containing electrode sheet by using the silicon-containing electrode sheet as the positive electrode and the lithium/copper metal composite electrode sheet as the negative electrode, and the in-situ electrochemical method is used to pre-store lithium.
其中，采用原位电化学方法预储锂，采用恒电流放电的方法，放电倍率为0.01C-10C，截止电压为0.2-0伏特；或是采用恒电压的方法，放电电压为0.2-0伏特，截止电流为0.001C-0.1C；或使用恒电流、恒电压组合放电的方法，恒电流条件，放电倍率为0.01C-10C，截止电压为0.2-0伏特，恒电压条件，放电电压为0.2-0伏特，截止电流为0.001C-0.1C。Among them, the in-situ electrochemical method is used to pre-store lithium, the method of constant current discharge is adopted, the discharge rate is 0.01C-10C, and the cut-off voltage is 0.2-0 volts; or the method of constant voltage is adopted, and the discharge voltage is 0.2-0 volts , the cut-off current is 0.001C-0.1C; or use the method of constant current and constant voltage combined discharge, constant current condition, discharge rate is 0.01C-10C, cut-off voltage is 0.2-0 volts, constant voltage condition, discharge voltage is 0.2 -0 volts, cut-off current is 0.001C-0.1C.
第三步中，所述气体保护环境为氮气或氩气保护环境。In the third step, the gas protection environment is nitrogen or argon protection environment.
本发明提供的基于含硅负极的锂硫电池的原位制备方法，通过三电极锂硫电池体系的建立，进行原位预储锂，该方法省去了拆电池、取出预储锂极片、并重复制备极片的过程，克服了拆电池、取出预储锂极片并重复制备极片的过程中的失效风险，简化了锂硫电池的制备流程，规避了过程失效风险。该制备方法工艺较简单，有利于锂硫电池的生产推广，具有重大生产实践意义。The in-situ preparation method of the lithium-sulfur battery based on the silicon-containing negative electrode provided by the present invention performs in-situ pre-storage of lithium through the establishment of a three-electrode lithium-sulfur battery system. And repeat the process of preparing the pole piece, overcome the failure risk in the process of dismantling the battery, taking out the pre-stored lithium pole piece and repeating the preparation of the pole piece, simplify the preparation process of the lithium-sulfur battery, and avoid the risk of process failure. The preparation method has a relatively simple process, is conducive to the production and promotion of lithium-sulfur batteries, and has great practical significance in production.
附图说明Description of drawings
图1为本发明实施例1的预储锂曲线；Fig. 1 is the pre-storage lithium curve of embodiment 1 of the present invention;
图2为本发明实施例1、3制备的三电极锂硫电池的示意图；2 is a schematic diagram of a three-electrode lithium-sulfur battery prepared in Examples 1 and 3 of the present invention;
图3为本发明实施例1、3制备的三电极锂硫电池的截面示意图；3 is a schematic cross-sectional view of a three-electrode lithium-sulfur battery prepared in Examples 1 and 3 of the present invention;
图4为本发明实施例1、2、3中最终制备的两极锂硫电池的截面示意图；Fig. 4 is a schematic cross-sectional view of the bipolar lithium-sulfur battery finally prepared in Examples 1, 2, and 3 of the present invention;
图5为本发明实施例2的预储锂曲线；Fig. 5 is the pre-storage lithium curve of embodiment 2 of the present invention;
图6为本发明实施例3的预储锂曲线。Fig. 6 is the pre-storage lithium curve of Example 3 of the present invention.
具体实施方式Detailed ways
下面，结合实例对本发明的实质性特点和优势作进一步的说明，但本发明并不局限于所列的实施例。Below, the substantive features and advantages of the present invention will be further described in conjunction with examples, but the present invention is not limited to the listed examples.
实施例1Example 1
一种基于含硅负极的锂硫电池的原位制备方法，锂/铜金属复合电极片中，铜箔作为金属锂的结构支撑、集流体和极耳来使用，含硅负极使用纯硅负极，实施例步骤如下：An in-situ preparation method of a lithium-sulfur battery based on a silicon-containing negative electrode. In a lithium/copper metal composite electrode sheet, copper foil is used as a structural support, current collector and tab for lithium metal, and a pure silicon negative electrode is used for the silicon-containing negative electrode. Embodiment steps are as follows:
(1)首先制备锂/铜金属复合电极片待用，该极片由金属锂箔和铜箔组成，将金属锂箔贴附于铜箔的两面并留出极耳(铜箔除极耳外的其它部分两面由金属锂箔覆盖)，制得所述锂/铜金属复合电极片；(1) First prepare the lithium/copper metal composite electrode sheet for use. The electrode sheet is composed of metal lithium foil and copper foil. The other parts of the two sides are covered by metal lithium foil), and the lithium/copper metal composite electrode sheet is obtained;
其中，锂箔的厚度为40微米，铜箔的厚度为8微米，锂箔/含硅电极片的容量比为3；Among them, the thickness of lithium foil is 40 microns, the thickness of copper foil is 8 microns, and the capacity ratio of lithium foil/silicon-containing electrode sheet is 3;
另外，按照锂硫电池的制备工艺流程，准备锂硫电池正极极片、含硅电极片、隔膜、极耳、电池壳、电解液等待用。In addition, according to the preparation process of the lithium-sulfur battery, prepare the lithium-sulfur battery positive electrode sheet, silicon-containing electrode sheet, separator, tab, battery case, and electrolyte for use.
需说明的是，锂硫电池正极极片、含硅电极片、隔膜、极耳、电池壳、电解液等均为常规材料或常规制备方法制备。It should be noted that the lithium-sulfur battery positive electrode sheet, silicon-containing electrode sheet, separator, tab, battery case, electrolyte, etc. are all conventional materials or conventional preparation methods.
(2)按照锂硫电池正极极片、锂/铜金属复合电极片、含硅电极片和锂/铜金属复合电极片的叠片顺序进行叠片，制备三电极锂硫叠片电池；(2) Lamination is carried out according to the lamination sequence of the lithium-sulfur battery positive electrode sheet, lithium/copper metal composite electrode sheet, silicon-containing electrode sheet and lithium/copper metal composite electrode sheet to prepare a three-electrode lithium-sulfur laminated battery;
电极叠片时，锂硫电池正极极片和含硅电极片的极耳在电池同一侧，作为电池的首侧，锂/铜电极片的极耳在首侧相对的一侧，作为电池的尾侧。When the electrodes are stacked, the tabs of the positive pole piece and the silicon-containing electrode piece of the lithium-sulfur battery are on the same side of the battery as the head side of the battery, and the tabs of the lithium/copper electrode piece are on the opposite side of the head side as the tail of the battery. side.
(3)使用原位电化学预储锂的方法，对含硅电极进行预储锂，电化学预处理，以含硅电极片为正极，以锂/铜复合电极片为负极，可以采用恒电流放电和恒压放电结合的方式，恒电流条件，放电倍率为0.1C，截止电压为0.005伏特，恒电压条件，放电电压为0.005伏特，截止电流为0.02C。(3) Use the method of in-situ electrochemical pre-storage of lithium to pre-storage lithium on the silicon-containing electrode, electrochemical pretreatment, use the silicon-containing electrode sheet as the positive electrode, and use the lithium/copper composite electrode sheet as the negative electrode, and a constant current can be used The method of combining discharge and constant voltage discharge, the constant current condition, the discharge rate is 0.1C, the cut-off voltage is 0.005 volts, the constant voltage condition, the discharge voltage is 0.005 volts, and the cut-off current is 0.02C.
(4)预储锂结束后，在氩气干燥环境下，将锂/铜金属复合电极片取出，然后对极组除气并进行直封，得到以含硅电极片为负极的两电极锂硫电池。(4) After the pre-storage of lithium is completed, the lithium/copper metal composite electrode sheet is taken out in an argon dry environment, and then the electrode group is degassed and directly sealed to obtain a two-electrode lithium-sulfur electrode sheet with a silicon-containing electrode sheet as the negative electrode. Battery.
实施例2Example 2
一种基于含硅负极的锂硫电池的原位制备方法，锂/铜金属复合电极片中，铜箔作为极耳来使用，含硅负极使用纯硅负极，实施例步骤如下：An in-situ preparation method of a lithium-sulfur battery based on a silicon-containing negative electrode. In a lithium/copper metal composite electrode sheet, copper foil is used as a tab, and a silicon-containing negative electrode is a pure silicon negative electrode. The steps of the embodiment are as follows:
(1)首先制备锂/铜金属复合电极片待用，该极片由金属锂箔和铜箔组成，将金属锂箔与作为极耳的铜箔相贴附，制得所述锂/铜金属复合电极片；(1) Firstly prepare a lithium/copper metal composite electrode sheet for use. The electrode sheet is composed of metal lithium foil and copper foil, and the metal lithium foil is attached to the copper foil as a tab to obtain the lithium/copper metal Composite electrode sheet;
其中，锂箔的厚度为200微米，铜箔的厚度为8微米，锂箔/含硅电极片的容量比为5；Among them, the thickness of lithium foil is 200 microns, the thickness of copper foil is 8 microns, and the capacity ratio of lithium foil/silicon-containing electrode sheet is 5;
另外，按照锂硫电池的制备工艺流程，准备锂硫电池正极极片、含硅电极片、隔膜、极耳、电池壳、电解液等待用；In addition, according to the preparation process of lithium-sulfur batteries, prepare lithium-sulfur battery positive pole pieces, silicon-containing electrode pieces, diaphragms, tabs, battery cases, and electrolytes for use;
需说明的是，锂硫电池正极极片、含硅电极片、隔膜、极耳、电池壳、电解液等均为常规材料或常规制备方法制备。It should be noted that the lithium-sulfur battery positive electrode sheet, silicon-containing electrode sheet, separator, tab, battery case, electrolyte, etc. are all conventional materials or conventional preparation methods.
(2)按照锂硫电池正极极片、锂/铜金属复合电极片、含硅电极片和锂/铜金属复合电极片的叠片顺序进行叠片，制备三电极锂硫叠片电池；(2) Lamination is carried out according to the lamination sequence of the lithium-sulfur battery positive electrode sheet, lithium/copper metal composite electrode sheet, silicon-containing electrode sheet and lithium/copper metal composite electrode sheet to prepare a three-electrode lithium-sulfur laminated battery;
电极叠片时，锂硫电池正极极片和含硅电极片的极耳在电池同一侧，作为电池的首侧，锂/铜电极片的极耳在首侧相对的一侧，作为电池的尾侧。When the electrodes are stacked, the tabs of the positive pole piece and the silicon-containing electrode piece of the lithium-sulfur battery are on the same side of the battery as the head side of the battery, and the tabs of the lithium/copper electrode piece are on the opposite side of the head side as the tail of the battery. side.
(3)使用原位电化学预储锂的方法，对含硅电极进行预储锂，电化学预处理，以含硅电极片为正极，以锂/铜复合电极片为负极，采用恒电流放电的方式，恒电流条件，放电倍率为0.05C，截止电压为0.001伏特。(3) Using the method of in-situ electrochemical pre-storage of lithium, pre-storage lithium on the silicon-containing electrode, electrochemical pretreatment, use the silicon-containing electrode sheet as the positive electrode, use the lithium/copper composite electrode sheet as the negative electrode, and use constant current discharge The way, the constant current condition, the discharge rate is 0.05C, and the cut-off voltage is 0.001 volts.
(4)预储锂结束后，在氩气干燥环境下，将锂/铜金属复合电极片取出，然后对极组除气并进行直封，得到以含硅电极片为负极的两电极锂硫电池。(4) After the pre-storage of lithium is completed, the lithium/copper metal composite electrode sheet is taken out in an argon dry environment, and then the electrode group is degassed and directly sealed to obtain a two-electrode lithium-sulfur electrode sheet with a silicon-containing electrode sheet as the negative electrode. Battery.
实施例3Example 3
一种基于含硅负极的锂硫电池的原位制备方法，锂/铜金属复合电极片中，铜箔作为金属锂的结构支撑、集流体和极耳来使用，含硅负极使用含6％硅材料的石墨负极，实施例步骤如下：An in-situ preparation method of a lithium-sulfur battery based on a silicon-containing negative electrode. In a lithium/copper metal composite electrode sheet, copper foil is used as a structural support, current collector, and tab for lithium metal. The silicon-containing negative electrode uses 6% silicon The graphite negative pole of material, embodiment steps are as follows:
(1)首先制备锂/铜金属复合电极片待用，该极片由金属锂箔和铜箔组成，将金属锂箔贴附于铜箔两面并留出极耳(铜箔除极耳外的其它部分两面由金属锂箔覆盖)，制得所述锂/铜金属复合电极片；(1) First prepare the lithium/copper metal composite electrode sheet for use. The electrode sheet is composed of metal lithium foil and copper foil. The two sides of other parts are covered by metal lithium foil), and the lithium/copper metal composite electrode sheet is obtained;
其中，锂箔的厚度为40微米，铜箔的厚度为8微米，锂箔/含硅电极片的容量比为3；Among them, the thickness of lithium foil is 40 microns, the thickness of copper foil is 8 microns, and the capacity ratio of lithium foil/silicon-containing electrode sheet is 3;
另外，按照锂硫电池的制备工艺流程，准备锂硫电池正极极片、含硅电极片、隔膜、极耳、电池壳、电解液等待用。In addition, according to the preparation process of the lithium-sulfur battery, prepare the lithium-sulfur battery positive electrode sheet, silicon-containing electrode sheet, separator, tab, battery case, and electrolyte for use.
需说明的是，锂硫电池正极极片、含硅电极片、隔膜、极耳、电池壳、电解液等均为常规材料或常规制备方法制备。It should be noted that the lithium-sulfur battery positive electrode sheet, silicon-containing electrode sheet, separator, tab, battery case, electrolyte, etc. are all conventional materials or conventional preparation methods.
(2)按照锂硫电池正极极片、锂/铜金属复合电极片、含硅电极片和锂/铜金属复合电极片的叠片顺序进行叠片，制备三电极锂硫叠片电池；(2) Lamination is carried out according to the lamination sequence of the lithium-sulfur battery positive electrode sheet, lithium/copper metal composite electrode sheet, silicon-containing electrode sheet and lithium/copper metal composite electrode sheet to prepare a three-electrode lithium-sulfur laminated battery;
电极叠片时，锂硫电池正极极片和含硅电极片的极耳在电池同一侧，作为电池的首侧，锂/铜电极片的极耳在首侧相对的一侧，作为电池的尾侧。When the electrodes are stacked, the tabs of the positive pole piece and the silicon-containing electrode piece of the lithium-sulfur battery are on the same side of the battery as the head side of the battery, and the tabs of the lithium/copper electrode piece are on the opposite side of the head side as the tail of the battery. side.
(3)使用原位电化学预储锂的方法，对含硅电极进行预储锂，电化学预处理，以含硅电极片为正极，以锂/铜复合电极片为负极，可以采用恒电流放电和恒压放电结合的方式，恒电流条件，放电倍率为0.1C，截止电压为0.005伏特，恒电压条件，放电电压为0.005伏特，截止电流为0.02C。(3) Use the method of in-situ electrochemical pre-storage of lithium to pre-storage lithium on the silicon-containing electrode, electrochemical pretreatment, use the silicon-containing electrode sheet as the positive electrode, and use the lithium/copper composite electrode sheet as the negative electrode, and a constant current can be used The method of combining discharge and constant voltage discharge, the constant current condition, the discharge rate is 0.1C, the cut-off voltage is 0.005 volts, the constant voltage condition, the discharge voltage is 0.005 volts, and the cut-off current is 0.02C.
(4)预储锂结束后，在氩气干燥环境下，将锂/铜金属复合电极片取出，然后对极组除气并进行直封，得到以含硅电极片为负极的两电极锂硫电池。(4) After the pre-storage of lithium is completed, the lithium/copper metal composite electrode sheet is taken out in an argon dry environment, and then the electrode group is degassed and directly sealed to obtain a two-electrode lithium-sulfur electrode sheet with a silicon-containing electrode sheet as the negative electrode. Battery.
图2示出了本发明实施例1、3制备的三电极锂硫电池的外形图，包括正极耳1、含硅电极片的硅负极极耳2以及锂/铜金属复合电极片的极耳3。Figure 2 shows the appearance of the three-electrode lithium-sulfur battery prepared in Examples 1 and 3 of the present invention, including the positive tab 1, the silicon negative tab 2 containing the silicon electrode sheet, and the tab 3 of the lithium/copper metal composite electrode sheet .
图3示出了本发明实施例1、3制备的三电极锂硫电池的截面图，包括有锂/铜金属复合电极片7、电池正极极片6以及含硅电极片5，锂/铜金属复合电极片7在电池正极极片6以及含硅电极片5之间，锂/铜金属复合电极片7、电池正极极片6以及含硅电极片5并由隔膜4隔开进行叠片。Figure 3 shows a cross-sectional view of a three-electrode lithium-sulfur battery prepared in Examples 1 and 3 of the present invention, including lithium/copper metal composite electrode sheet 7, battery positive electrode sheet 6, and silicon-containing electrode sheet 5, lithium/copper metal The composite electrode sheet 7 is between the battery positive electrode sheet 6 and the silicon-containing electrode sheet 5 .
需要说明的是，如果铜箔仅作为极耳使用时，在实施例2中的情形，则在图3中的锂/铜金属复合电极片7为由锂片来取代，实施例2中制备的三电极锂硫电池的截面图其它结构如图2所示。It should be noted that if the copper foil is only used as a tab, in the case of Example 2, the lithium/copper metal composite electrode sheet 7 in Figure 3 is replaced by a lithium sheet, prepared in Example 2 The other structures of the cross-sectional view of the three-electrode lithium-sulfur battery are shown in Fig. 2 .
图4示出了示出了本发明实施例1、2、3制备的锂硫电池的截面图,包括含硅电极片5、电池正极极片6以及将含硅电极片5与电池正极极片6之间隔开的隔膜4。Fig. 4 shows the cross-sectional view of the lithium-sulfur battery prepared by Examples 1, 2, and 3 of the present invention, including the silicon-containing electrode sheet 5, the positive electrode sheet 6 of the battery, and the silicon-containing electrode sheet 5 and the positive electrode sheet of the battery. 6 separated by a diaphragm 4 .
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.
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