CN106785075B - A kind of in-situ preparation method of lithium-sulfur battery based on graphite negative electrode - Google Patents
A kind of in-situ preparation method of lithium-sulfur battery based on graphite negative electrode Download PDFInfo
- Publication number
- CN106785075B CN106785075B CN201611165019.7A CN201611165019A CN106785075B CN 106785075 B CN106785075 B CN 106785075B CN 201611165019 A CN201611165019 A CN 201611165019A CN 106785075 B CN106785075 B CN 106785075B
- Authority
- CN
- China
- Prior art keywords
- lithium
- electrode sheet
- graphite
- preparation
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 56
- 239000010439 graphite Substances 0.000 title claims abstract description 56
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 115
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052802 copper Inorganic materials 0.000 claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000003860 storage Methods 0.000 claims abstract description 18
- 238000003475 lamination Methods 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 59
- 239000002905 metal composite material Substances 0.000 claims description 34
- 239000011889 copper foil Substances 0.000 claims description 22
- 239000011888 foil Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 5
- -1 copper metal compound Chemical class 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 239000002131 composite material Substances 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
- 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
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
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- 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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Connection Of Batteries Or Terminals (AREA)
Abstract
Description
技术领域technical field
本发明属于锂硫电池技术领域，涉及一种基于石墨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 lithium-sulfur batteries based on graphite negative electrodes.
背景技术Background technique
近年来，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，对二次电池的需求增加，特别的，对电池能量密度要求越来越高，以适应能源存储设备更简洁、更轻便的发展趋势。In recent years, with the rapid development of consumer electronics, new energy vehicles and energy storage systems, the demand for secondary batteries has increased. In particular, the requirements for battery energy density have become higher and higher to adapt to energy storage devices that are more compact and The trend towards lighter weight.
锂硫电池是以硫元素作为电池正极的一种锂电池。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。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，锂硫电池是一种非常有前景的锂电池。A lithium-sulfur battery is a lithium battery that uses sulfur as the positive electrode of the battery. The specific capacity is as high as 1675mAh/g, which is much higher than that of the lithium cobalt oxide battery widely used in commerce. And sulfur is an element that is friendly to the environment and has basically no pollution to the environment. Considering the low cost of sulfur, lithium-sulfur batteries are a very promising lithium battery.
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，多硫化合物与锂金属负极反应，易造成穿梭效应，导致活性物质损失，影响循环性能。Lithium-sulfur batteries use sulfur-based compounds with sulfur-sulfur bonds as positive electrode active materials. Lithium polysulfide compounds dissolve in the electrolyte, and polysulfide compounds react with lithium metal negative electrodes, which can easily cause shuttle effects, resulting in loss of active materials and 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。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.
采用石墨负极替代金属锂负极制备锂硫电池，克服了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。Using graphite anode instead of metal lithium anode to prepare lithium-sulfur batteries overcomes the high chemical instability of metal lithium and the generation of lithium dendrites, and 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
本发明的目的是提供一种基于石墨负极的锂硫电池的原位制备方法。该制备方法可控性高，简化了石墨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 graphite negative electrode. The preparation method has high controllability, simplifies the preparation process of the graphite-based lithium-sulfur battery, avoids the failure risk of the existing process, and is easily transformed into an industrial production technology.
为实现上述目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
本发明是这样实现的，一种基于石墨负极的锂硫电池的原位制备方法，包括以下步骤：The present invention is realized in this way, a kind of in-situ preparation method of lithium-sulfur battery based on graphite negative pole, comprises the following steps:
第一步：制备锂/铜金属复合电极片，该锂/铜金属复合电极片包括铜箔以及贴附于铜箔之上的金属锂制成的作为锂源的锂箔；The first step: preparing a lithium/copper metal composite electrode sheet, the lithium/copper metal composite electrode sheet includes copper foil and a lithium foil made of metal 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、石墨电极片和锂/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, graphite 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石墨电极片进行预储锂；Step 3: Pre-store lithium on the graphite electrode sheet by using the method of in-situ electrochemical pre-storage of lithium;
第四步：预储锂结束后，在保护气氛环境下，将锂/铜金属复合电极片取出，然后对极组除气并进行直封，得到以石墨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 protective atmosphere, and then the electrode group is degassed and directly sealed to obtain a two-electrode lithium-sulfur battery with the graphite 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/石墨电极片的容量比为1-10；所述铜箔作为极耳使用时，锂箔/石墨电极片的容量比为2-10。When the copper foil is used as the structural support, current collector and tab of metal lithium, the capacity ratio of the lithium foil/graphite electrode sheet is 1-10; when the copper foil is used as the tab, the capacity ratio of the lithium foil/graphite electrode sheet The capacity ratio 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.
第二步中，电极叠片时，锂硫电池正极极片和石墨电极片的极耳在电池同一侧，作为电池的首侧；锂/铜金属复合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 electrode sheet and the graphite electrode sheet of the lithium-sulfur battery are on the same side of the battery as the first side of the battery; the tabs of the lithium/copper metal composite electrode sheet are on the opposite side of the first side. side, as the tail side of the battery.
第三步中，对石墨电极片进行预储锂是以石墨电极片为正极，以锂/铜金属复合电极片为负极，采用电化学方法预储锂。In the third step, lithium is pre-stored on the graphite electrode sheet by using the graphite electrode sheet as the positive electrode and the lithium/copper metal composite electrode sheet as the negative electrode, and the electrochemical method is used to pre-store lithium.
第三步中，采用电化学方法预储锂的方法，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。In the third step, the method of pre-storing lithium by electrochemical method is adopted, 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. 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 conditions, the discharge rate is 0.01C-10C, the cut-off voltage is 0.2-0 volts, constant voltage conditions, discharge voltage It is 0.2-0 volts, and the cut-off current is 0.001C-0.1C.
第四步中，所述保护气氛环境是指氮气或氩气。In the fourth step, the protective atmosphere refers to nitrogen or argon.
本发明提供的基于石墨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。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 graphite negative electrode provided by the present invention, through the establishment of the three-electrode lithium-sulfur battery system, performs in-situ pre-storage of lithium. Repeating the process of preparing pole pieces overcomes the risk of failure in the process of dismantling the battery, taking out the pre-stored lithium pole piece and repeating the preparation of the pole piece, and simplifies the preparation process of the lithium-sulfur battery. 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制备的锂/铜箔金属复合电极片的示意图；1 is a schematic diagram of a lithium/copper foil metal composite electrode sheet prepared in Example 1 of the present invention;
图2为本发明实施例1的预储锂曲线；Fig. 2 is the pre-storage lithium curve of embodiment 1 of the present invention;
图3为本发明实施例1制备的三电极锂硫电池的外形示意图；3 is a schematic diagram of the appearance of the three-electrode lithium-sulfur battery prepared in Example 1 of the present invention;
图4为本发明实施例1制备的三电极锂硫电池截面示意图；4 is a schematic cross-sectional view of a three-electrode lithium-sulfur battery prepared in Example 1 of the present invention;
图5为本发明实施例1中最终制备的锂硫电池截面示意图；5 is a schematic cross-sectional view of the lithium-sulfur battery finally prepared in Example 1 of the present invention;
图6为本发明实施例1中最终制备的锂硫电池的外形示意图；6 is a schematic diagram of the appearance of the lithium-sulfur battery finally prepared in Example 1 of the present invention;
图7为本发明实施例2制备的锂/铜极耳金属复合电极片的示意图；7 is a schematic diagram of a lithium/copper tab metal composite electrode sheet prepared in Example 2 of the present invention;
图8为本发明实施例2的预储锂曲线。Fig. 8 is the pre-storage lithium curve of Example 2 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
一种基于石墨负极的锂硫电池的原位制备方法，锂/铜金属复合电极片中，铜箔作为锂金属的结构支撑、集流体和极耳来使用，实施例步骤如下：An in-situ preparation method of a lithium-sulfur battery based on a graphite negative electrode. In a lithium/copper metal composite electrode sheet, copper foil is used as a structural support, current collector and tab of lithium metal. The steps of the embodiment are as follows:
(1)首先制备锂/铜金属复合电极片待用，该极片由金属锂制作成的锂箔2和铜箔1组成，将金属锂箔贴附于铜箔1两面并留出极耳(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；其中，锂箔的厚度为40微米，铜箔的厚度为8微米，锂箔/石墨电极片的容量比为3；(1) Firstly prepare a lithium/copper metal composite electrode sheet for use. The electrode sheet is composed of a lithium foil 2 and a copper foil 1 made of lithium metal. The lithium metal foil is attached to both sides of the copper foil 1 and the tabs are left ( The other parts of the copper foil except the tabs are covered by metallic lithium foil on both sides) to obtain the lithium/copper metal composite electrode sheet; wherein, the thickness of the lithium foil is 40 microns, the thickness of the copper foil is 8 microns, and the lithium foil/ The capacity ratio of the graphite 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、石墨电极片、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 electrode sheets, graphite electrode sheets, diaphragms, tabs, battery cases, and electrolytes for use.
需说明的是，锂硫电池正极极片、石墨电极片、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, graphite electrode sheet, separator, tab, battery case, electrolyte, etc. are all prepared by 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、石墨电极片和锂/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；外形如图3所示，包括正极耳3、石墨负极片的石墨负极极耳4以及锂/铜金属复合电极片的极耳5，其截面图如图4所示，包括石墨电极片6、正极片7以及锂/铜金属复合电极片8，锂/铜金属复合电极片8置于石墨电极片6、正极片7之间并由隔膜9相互隔开。(2) Laminate according to the lamination sequence of the lithium-sulfur battery positive electrode sheet, lithium/copper metal composite electrode sheet, graphite electrode sheet and lithium/copper metal composite electrode sheet to prepare a three-electrode lithium-sulfur laminated battery; the appearance is shown in the figure 3, including the positive tab 3, the graphite negative tab 4 of the graphite negative sheet, and the tab 5 of the lithium/copper metal composite electrode sheet, its cross-sectional view is shown in Figure 4, including the graphite electrode sheet 6, the positive sheet 7 and The lithium/copper metal composite electrode sheet 8, the lithium/copper metal composite electrode sheet 8 is placed between the graphite electrode sheet 6 and the positive electrode sheet 7 and separated from each other by a diaphragm 9.
电极叠片时，锂硫电池正极极片和石墨电极片的极耳在电池同一侧，作为电池的首侧，锂/铜金属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 electrode sheet and the graphite electrode sheet of the lithium-sulfur battery are on the same side of the battery as the first side of the battery, and the tabs of the lithium/copper metal electrode sheet are on the opposite side of the first side as the tail of the battery. side.
(3)使用原位电化学预储锂的方法，对石墨电极进行预储锂，电化学预处理，以石墨电极片为正极，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) Using the method of in-situ electrochemical pre-storage of lithium, the graphite electrode is pre-stored lithium, electrochemical pretreatment, the graphite electrode sheet is used as the positive electrode, and the lithium/copper composite electrode sheet is used as the negative electrode. Constant current discharge and The method of constant voltage discharge combination, constant current condition, discharge rate is 0.1C, cut-off voltage is 0.005 volts, constant voltage condition, discharge voltage is 0.005 volts, 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，得到以石墨电极片为负极的两电极锂硫电池，其截面图如图5所示，包括石墨电极片6、正极片7以及隔膜9，石墨电极片6、正极片7由隔膜9隔开，外形如图6所示，包括正极耳3以及石墨电极负极耳4。(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 battery with graphite electrode sheet as the negative electrode , its cross-sectional view is shown in Figure 5, including graphite electrode sheet 6, positive electrode sheet 7 and diaphragm 9, graphite electrode sheet 6, positive electrode sheet 7 are separated by diaphragm 9, and its appearance is shown in Figure 6, including positive electrode tab 3 and graphite Electrode negative ear 4.
实施例2Example 2
一种基于石墨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，实施例步骤如下：An in-situ preparation method of a lithium-sulfur battery based on a graphite negative electrode. In a lithium/copper metal composite electrode sheet, copper foil is used as a tab. The steps of the embodiment are as follows:
(1)首先制备锂/铜金属复合电极片待用，该极片由金属锂制成的锂箔2和铜箔形成的铜极耳1组成，将金属锂箔与作为极耳的铜箔贴附，制得所述锂/铜金属复合电极片；其中，锂箔的厚度为200微米，铜箔的厚度为8微米，锂箔/石墨电极的容量比为5；(1) First prepare the lithium/copper metal composite electrode sheet for use. The electrode sheet is composed of a lithium foil 2 made of metal lithium and a copper tab 1 formed by copper foil. The lithium metal foil is pasted with the copper foil as the tab. Attached, the lithium/copper metal composite electrode sheet is obtained; wherein, the thickness of the lithium foil is 200 microns, the thickness of the copper foil is 8 microns, and the capacity ratio of the lithium foil/graphite electrode 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、石墨电极片、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 electrode sheets, graphite electrode sheets, diaphragms, tabs, battery cases, and electrolytes for use.
需说明的是，锂硫电池正极极片、石墨电极片、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, graphite electrode sheet, separator, tab, battery case, electrolyte, etc. are all prepared by 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、石墨电极片和锂/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, graphite 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石墨电极片的极耳在电池同一侧，作为电池的首侧，锂/铜金属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 electrode sheet and the graphite electrode sheet of the lithium-sulfur battery are on the same side of the battery as the first side of the battery, and the tabs of the lithium/copper metal electrode sheet are on the opposite side of the first side as the tail of the battery. side.
(3)使用原位电化学预储锂的方法，对石墨电极进行预储锂，电化学预处理，以石墨电极片为正极，以锂/铜金属复合电极片为负极，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) Use the method of in-situ electrochemical pre-storage of lithium to pre-storage lithium on the graphite electrode, electrochemical pretreatment, use the graphite electrode sheet as the positive electrode, use the lithium/copper metal composite electrode sheet as the negative electrode, and use a constant current discharge method The method is 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，得到以石墨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 battery with graphite electrode sheet as the negative electrode .
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.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611165019.7A CN106785075B (en) | 2016-12-16 | 2016-12-16 | A kind of in-situ preparation method of lithium-sulfur battery based on graphite negative electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611165019.7A CN106785075B (en) | 2016-12-16 | 2016-12-16 | A kind of in-situ preparation method of lithium-sulfur battery based on graphite negative electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106785075A CN106785075A (en) | 2017-05-31 |
| CN106785075B true CN106785075B (en) | 2019-09-03 |
Family
ID=58891693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611165019.7A Active CN106785075B (en) | 2016-12-16 | 2016-12-16 | A kind of in-situ preparation method of lithium-sulfur battery based on graphite negative electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106785075B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4542723A4 (en) * | 2022-11-18 | 2025-12-31 | Lg Energy Solution Ltd | METHOD FOR MANUFACTURING A SECONDARY BATTERY |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107819104B (en) * | 2017-09-27 | 2020-06-26 | 天津力神电池股份有限公司 | Preparation method of lithium-copper composite negative electrode foil |
| US20200395593A1 (en) * | 2019-06-12 | 2020-12-17 | A123 Systems Llc | Anode pre-lithiation for high energy li-ion battery |
| CN111366852A (en) * | 2020-03-26 | 2020-07-03 | 上海电气集团股份有限公司 | In-situ observation method and device for charging state of graphite electrode |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102290614A (en) * | 2011-07-21 | 2011-12-21 | 东莞新能源科技有限公司 | A kind of lithium ion battery and the method for increasing its capacity |
| KR20120061529A (en) * | 2010-12-03 | 2012-06-13 | 현대자동차주식회사 | Lithium ion-sulfur battery |
| CN102694196A (en) * | 2012-05-16 | 2012-09-26 | 大连丽昌新材料有限公司 | Lithium sulphur battery and manufacturing method thereof |
| WO2016159058A1 (en) * | 2015-03-30 | 2016-10-06 | 日立化成株式会社 | Lithium ion secondary battery and method of manufacturing same |
-
2016
- 2016-12-16 CN CN201611165019.7A patent/CN106785075B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120061529A (en) * | 2010-12-03 | 2012-06-13 | 현대자동차주식회사 | Lithium ion-sulfur battery |
| CN102290614A (en) * | 2011-07-21 | 2011-12-21 | 东莞新能源科技有限公司 | A kind of lithium ion battery and the method for increasing its capacity |
| CN102694196A (en) * | 2012-05-16 | 2012-09-26 | 大连丽昌新材料有限公司 | Lithium sulphur battery and manufacturing method thereof |
| WO2016159058A1 (en) * | 2015-03-30 | 2016-10-06 | 日立化成株式会社 | Lithium ion secondary battery and method of manufacturing same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4542723A4 (en) * | 2022-11-18 | 2025-12-31 | Lg Energy Solution Ltd | METHOD FOR MANUFACTURING A SECONDARY BATTERY |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106785075A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104008893B (en) | The preparation method of lithium ion hybrid capacitors and lithium ion hybrid capacitors thereof | |
| CN103904290B (en) | Aquo-lithium ion battery combination electrode and preparation method thereof, aquo-lithium ion battery | |
| CN203707250U (en) | Lithium battery | |
| CN101465441B (en) | A kind of preparation method of lithium-sulfur battery using graphite as negative electrode | |
| CN207611809U (en) | Lithium-ion battery positive pole piece and lithium-ion battery | |
| CN103187551A (en) | Lithium ion liquid flow battery | |
| CN106450467A (en) | Lithium supplementing method for energy storage device | |
| CN104795559A (en) | High-energy-density lithium-ion battery | |
| CN106785075B (en) | A kind of in-situ preparation method of lithium-sulfur battery based on graphite negative electrode | |
| CN103515595A (en) | Sulfur/polypyrrole-graphene composite material, preparation method thereof, battery positive electrode and lithium-sulfur battery | |
| CN109428138B (en) | Preparation method of lithium-air battery and lithium-air battery | |
| WO2018059180A1 (en) | High-power, high-energy chemical power supply and preparation method therefor | |
| CN105977526A (en) | Rechargeable aluminum carbon battery and preparation method thereof | |
| CN106450487B (en) | A kind of in-situ preparation method of lithium-sulfur cell structure | |
| CN206834275U (en) | A kind of high multiplying power lithium ion battery | |
| CN105449271A (en) | Aluminium ion secondary battery taking CuS as cathode and preparation technology thereof | |
| CN110364771A (en) | Aqueous zinc ion soft pack battery and preparation method thereof | |
| CN106450488B (en) | A kind of in-situ preparation method of lithium-sulfur battery based on silicon negative electrode | |
| CN105552379A (en) | Preparation method of silicon anode lithium-ion battery employing carbon nanotube paper as current collector | |
| CN108511855A (en) | A kind of Li/Na-O of Li/Na composite metal negative poles2Secondary cell | |
| CN106450489B (en) | An in-situ preparation method for lithium-sulfur batteries based on hard carbon negative electrodes | |
| CN202917600U (en) | Aluminum-plastic packed high-power lithium ion battery | |
| CN109244335A (en) | A kind of polyimide diaphragm lithium-sulfur cell and preparation method thereof | |
| WO2020124328A1 (en) | Pre-lithiated negative electrode fabrication method, fabricated pre-lithiated negative electrode, energy storage device, energy storage system, and electrical device | |
| CN101409361A (en) | Composite cathode material lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230202 Address after: 300457 No. 38, Haitai South Road, Binhai high tech Industrial Development Zone (outer ring), Binhai New Area, Tianjin Patentee after: TIANJIN LISHEN BATTERY JOINT-STOCK Co.,Ltd. Patentee after: Tianjin Juyuan New Energy Technology Co.,Ltd. Address before: 300384 Tianjin Xiqing District Binhai hi tech Industrial Development Zone (outer ring) 38 Haitai South Road Patentee before: TIANJIN LISHEN BATTERY JOINT-STOCK Co.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 300457 No. 38, Haitai South Road, Binhai high tech Industrial Development Zone (outer ring), Binhai New Area, Tianjin Patentee after: TIANJIN LISHEN BATTERY JOINT-STOCK Co.,Ltd. Country or region after: China Patentee after: Tianjin Lishen Juyuan New Energy Technology Co.,Ltd. Address before: 300457 No. 38, Haitai South Road, Binhai high tech Industrial Development Zone (outer ring), Binhai New Area, Tianjin Patentee before: TIANJIN LISHEN BATTERY JOINT-STOCK Co.,Ltd. Country or region before: China Patentee before: Tianjin Juyuan New Energy Technology Co.,Ltd. |