CN112331904A - Lithium-free negative electrode-lithium secondary battery and preparation method thereof - Google Patents
Lithium-free negative electrode-lithium secondary battery and preparation method thereof Download PDFInfo
- Publication number
- CN112331904A CN112331904A CN202011067121.XA CN202011067121A CN112331904A CN 112331904 A CN112331904 A CN 112331904A CN 202011067121 A CN202011067121 A CN 202011067121A CN 112331904 A CN112331904 A CN 112331904A
- Authority
- CN
- China
- Prior art keywords
- lithium
- negative electrode
- secondary battery
- electrolyte
- free negative
- 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.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000003792 electrolyte Substances 0.000 claims abstract description 47
- 239000000126 substance Substances 0.000 claims abstract description 32
- 230000000694 effects Effects 0.000 claims abstract description 15
- 210000001787 dendrite Anatomy 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 4
- 239000013067 intermediate product Substances 0.000 claims abstract description 4
- 238000006479 redox reaction Methods 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 239000011889 copper foil Substances 0.000 claims description 18
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011149 active material Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 14
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002000 Electrolyte additive Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 4
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 229910013553 LiNO Inorganic materials 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明属于无锂负极全电池相关技术领域，其公开了一种无锂负极‑锂二次电池及其制备方法，所述电池采用改性电解液，所述改性电解液内添加有微量物质，所述微量物质能够产生穿梭效应，该微量物质在该电池的正负极之间来回穿梭并发生电化学及化学反应来消除锂枝晶以及活化死锂；所述微量物质及其中间产物能溶解于所述电解液中，并能在电池工作电压区间分别与负极及正极发生还原反应及氧化反应，最终回到初始状态。本发明能有效消除锂枝晶与活化死锂，减小界面阻抗，很大程度上避免了活性物质锂的损失，因此能有效提升无锂负极‑锂二次电池的综合性能。
The invention belongs to the related technical field of a lithium-free negative electrode full battery, and discloses a lithium-free negative electrode-lithium secondary battery and a preparation method thereof. The battery adopts a modified electrolyte, and the modified electrolyte is added with trace substances , the trace substances can produce a shuttle effect, the trace substances shuttle back and forth between the positive and negative electrodes of the battery and undergo electrochemical and chemical reactions to eliminate lithium dendrites and activate dead lithium; the trace substances and their intermediate products can It is dissolved in the electrolyte, and can undergo reduction reaction and oxidation reaction with the negative electrode and the positive electrode respectively in the battery working voltage range, and finally return to the initial state. The present invention can effectively eliminate lithium dendrites and activated dead lithium, reduce the interface impedance, and largely avoid the loss of active material lithium, so that the comprehensive performance of the lithium-free negative electrode-lithium secondary battery can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of lithium-free cathode full batteries, and particularly relates to a lithium-free cathode-lithium secondary battery and a preparation method thereof.
Background
At present, most of commercialized secondary lithium ion batteries are prepared by matching layered transition metal oxides with lithium sources and graphite, but the development of the energy density of the secondary lithium ion batteries is gradually close to the theoretical threshold value, and further breakthrough is difficult to occur.
Lithium metal has an extremely high specific capacity (3860mAh g)-1) And the lowest standard hydrogen potential (-3.04V) to become a very potential negative electrode of choice in next generation batteries. However, lithium metal in practical use suffers from a number of problems including the formation and growth of lithium dendrites, the uninterrupted side reactions with the electrolyte resulting in low coulombic efficiency and the formation of dead lithium after the dendrites overgrow out of electrical contact increasing the interfacial resistance. In order to cover these problems, many studies today use an excessive amount of lithium source as a negative electrode, which can compensate for the loss of active lithium during the cycling of the battery, thereby greatly improving the performance of the battery, but at the same time, the use of the excessive amount of lithium source reduces the energy density of the battery as a whole, which is contrary to the original purpose of using metal lithium as a negative electrode.
The proposal of a lithium-free negative electrode-lithium secondary battery is advantageous for solving such problems. In such a battery, the negative electrode is composed of only the current collector, the positive electrode is composed of a material with a lithium source, and all the lithium source in the battery system comes from the positive electrode, so that no excessive lithium source exists. When the battery is charged in the first circle, lithium ions are extracted from the positive electrode, and are conducted by the electrolyte and then deposited on the negative electrode to form metal lithium, and the subsequent circulation process is consistent with that of a common lithium metal battery. However, the overall performance of such batteries is often poor, and since no excessive lithium exists, a part of lithium is inevitably lost during the cycling process of the batteries, especially during the first charging process, and the capacity corresponding to the part of lithium is also lost irreversibly, so that the lost capacity is accumulated continuously with the increase of the cycling time, and finally, the charging and discharging capacity and the cycling performance of the batteries are greatly influenced. Meanwhile, the overgrowth of lithium dendrites can bring about serious safety hazards. Therefore, designing a method capable of effectively improving the comprehensive performance of the lithium-free cathode-lithium secondary battery is of great significance to the practical application of the battery.
Disclosure of Invention
Aiming at the defects or improvement requirements in the prior art, the invention provides a lithium-free cathode-lithium secondary battery and a preparation method thereof, wherein a trace of substance capable of generating a shuttle effect in the charging and discharging processes of the battery is added into electrolyte so as to improve the comprehensive performance of the battery, including charging and discharging capacity, cycle life, safety and the like, and the trace of substance capable of generating the shuttle effect can react with lithium dendrite or inactive lithium (dead lithium) on the cathode side to generate a reduction reaction when the battery works; the generated product is diffused to the positive electrode side in the electrolyte, oxidation reaction occurs and the product returns to the initial state, and in the process, the substance is unchanged, but lithium dendrite and dead lithium can be effectively eliminated, interface impedance is reduced, and loss of active substance lithium is avoided to a great extent, so that the comprehensive performance of the lithium-free negative electrode-lithium secondary battery can be effectively improved.
In order to achieve the above object, according to one aspect of the present invention, there is provided a lithium-free negative-electrode secondary battery, wherein a modified electrolyte is used in the battery, and a trace substance is added in the modified electrolyte, and the trace substance is capable of generating a shuttle effect, and shuttles back and forth between a positive electrode and a negative electrode of the battery and performs electrochemical and chemical reactions to eliminate lithium dendrites and activate dead lithium; the trace substances and the intermediate products thereof can be dissolved in the electrolyte, and can respectively perform reduction reaction and oxidation reaction with the cathode and the anode in the working voltage interval of the battery, and finally return to the initial state.
Further, the trace species comprises iodine, polyiodide, lithium iodide, and lithium polysulfide.
Further, the lithium-free negative electrode of the battery is composed of a metallic current collector.
Further, the metal current collector is composed of a copper foil.
Further, the positive electrode of the battery is a lithium-containing positive electrode.
Further, the positive electrode comprises lithium iron phosphate, lithium cobaltate and nickel cobalt manganese lithium.
Further, the concentration of the trace substance in the modified electrolyte is less than 0.5M.
Further, the concentration of the trace substance is less than 0.1M.
According to another aspect of the present invention, there is provided a method of manufacturing the lithium-free negative electrode-lithium secondary battery as described above.
Further, a trace amount of substance was added to the electrolyte, and the mixture was stirred on a magnetic stirring table at room temperature until completely dissolved, thereby obtaining the modified electrolyte.
In general, compared with the prior art, the lithium-free negative electrode-lithium secondary battery and the preparation method thereof provided by the invention have the following beneficial effects:
1. the invention can effectively eliminate the lithium dendrite by utilizing the shuttle effect and activate the dead lithium without electronic contact, thereby effectively improving the comprehensive properties of the lithium-free cathode-lithium secondary battery, including charge and discharge capacity, cycle life and safety.
2. The method is simple and low in cost, and only a trace amount of substances capable of generating the shuttle effect need to be added into the existing electrolyte system.
3. The invention can effectively ensure the inherent energy density advantage of the system while improving the comprehensive performance of the lithium-free cathode full cell, and compared with other improving modes, the invention introduces little quality of other components.
4. The concentration of the trace substance is below 0.5M, and more preferably below 0.1M, so that the trace substance can generate a certain shuttling effect, and the battery cannot be disabled due to a serious shuttling effect.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) characterization of lithium deposition on copper foil after first charge of an assembled full cell according to preferred embodiment 2 of the present invention;
fig. 2 is an SEM characterization of lithium deposition on copper foil after first-pass discharge of an assembled full cell according to preferred embodiment 2 of the present invention;
fig. 3 is a Scanning Electron Microscope (SEM) characterization of lithium deposition on copper foil after first charge of a full cell assembled according to comparative example 1 of the present invention;
fig. 4 is an SEM characterization of lithium deposition on copper foil after first discharge of an assembled full cell according to comparative example 1 of the present invention;
fig. 5 is a graph comparing long cycle performance of the full cell assembled according to example 5 of the preferred embodiment 2 of the present invention with that of the full cell of comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The lithium-free cathode-lithium secondary battery and the preparation method thereof provided by the invention have the advantages that the battery adopts modified electrolyte, trace substances are added in the modified electrolyte, the trace substances can generate a shuttle effect, and the trace substances shuttle back and forth between the anode and the cathode of the battery and generate electrochemical and chemical reactions to eliminate lithium dendrites and activate dead lithium; the trace substances and the intermediate products thereof can be dissolved in the electrolyte, and can respectively perform reduction reaction and oxidation reaction with the cathode and the anode in the working voltage interval of the battery, and finally return to the initial state.
The trace substance comprises iodine, polyiodide, lithium iodide and lithium polysulfide. The lithium-free negative electrode of the battery is composed of a metal current collector, preferably, the metal current collector is composed of copper foil. The positive electrode of the battery is a lithium-containing positive electrode, and preferably, the components of the positive electrode comprise lithium iron phosphate, lithium cobaltate, lithium nickel cobalt manganese and the like.
The concentration of the trace species in the modified electrolyte needs to be such as to produce some shuttling effect, but not so high as to render the cell inoperable due to severe shuttling effect. Preferably, the concentration of the trace substance is 0.5M or less, and more preferably, the concentration thereof is 0.1M or less.
The present invention also provides a method for preparing a lithium-free negative electrode-lithium secondary battery, which is used for preparing the lithium-free negative electrode-lithium secondary battery, wherein trace substances are added into the electrolyte and are placed on a magnetic stirring table at room temperature to be stirred until the substances are completely dissolved, and preferably:
(a) an appropriate amount of lithium iodide powder was added to a commercial ether electrolyte [1M lithium bistrifluoromethylsulfonimide (LiTFSI) and 0.2M lithium nitrate (LiNO)3) Dissolving in 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME)]Or an ester electrolyte [1M lithium hexafluorophosphate (LiPF6) dissolved in Ethylene Carbonate (EC), diethyl carbonate (DEC) and fluoroethylene carbonate (FEC, 5%)]Placing the mixture on a magnetic stirring table at room temperature, and stirring until the mixture is completely dissolved to obtain a modified electrolyte;
(b) appropriate amounts of sulfur powder and lithium sulfide powder were added to a commercial ether electrolyte [1M lithium bistrifluoromethylsulfonimide (LiTFSI) and 0.2M lithium nitrate (LiNO)3) Dissolving in 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME)]And (4) placing the mixture on a magnetic stirring table at room temperature, and stirring until the mixture is completely dissolved, thereby obtaining the modified electrolyte.
And secondly, assembling the positive electrode, the negative electrode, the diaphragm, the modified electrolyte and the like together to obtain the lithium-free negative electrode-lithium secondary battery with improved comprehensive performance.
The analytical test method and the assembly and test process of the lithium iron phosphate full cell used in the following examples are as follows:
(1) scanning Electron Microscope (SEM) testing: the instrument model of the scanning electron microscope is FESEM, FEI Quanta 650; sample preparation and test methods: in a glove box filled with argon and having water and oxygen contents lower than 0.1ppm, the battery after the first charge cycle was disassembled, the negative electrode on which lithium had been deposited was taken out, washed with dimethyl ether glycol (DME) and dried, and then stuck to a sample stage, and then hermetically transferred to an apparatus for testing.
(2) Preparing modified electrolyte: in a glove box filled with argon and having a water and oxygen content below 0.1ppm, 0.025M, 0.05M lithium iodide (LiI) powder was added to commercial ethers [1M lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) and 0.2M lithium nitrate (LiNO), respectively3) Dissolving in 1, 3-Dioxolane (DOL) or ethylene glycol dimethyl ether (DME)]And esters [1M lithium hexafluorophosphate (LiPF)6) Dissolved in Ethylene Carbonate (EC), diethyl carbonate (DEC) and fluoroethylene carbonate (FEC, 5%)]Stirring the formed electrolyte on a magnetic stirring table at room temperature until the electrolyte is completely dissolved to prepare four electrolytes, namely 0.025M-LiI-ether, 0.05M-LiI-ether, 0.025M-LiI-ester and 0.05-LiI-ester; 0.025M lithium sulfide (Li) was added separately2S) powder with 0.1M Sulfur (S) powder, 0.05M lithium sulfide (Li)2S) powder with 0.2M Sulfur (S) powder to commercial ethers [1M lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) and 0.2M lithium nitrate (LiNO)3) Dissolving in 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME)]The electrolyte is placed on a magnetic stirring table at room temperature and stirred until the electrolyte is completely dissolved, and the electrolyte is prepared into 0.025M-Li2S5-ether, 0.05M-Li2S5-ether two electrolytes.
(3) Assembling a lithium-free negative electrode full battery: and (3) using commercial lithium iron phosphate as a positive electrode and commercial copper foil as a negative electrode, and respectively adopting the 6 modified electrolytes to assemble the battery.
(4) Testing of a lithium-free negative electrode full cell: the test uses a Land tester, the charging and discharging interval is 2.5-3.8V (ether) or 2.5-4.0V (ester), the cycle rate is 0.5C, and the battery test temperature is room temperature (25 ℃).
The present invention will be further illustrated with reference to specific examples.
Example 1
And (3) assembling the lithium-free negative electrode full battery by using the electrolyte solution I0.025M-LiI-ether, and performing charge and discharge tests on the battery at room temperature according to a set charge and discharge program.
Example 2
And assembling the lithium-free cathode full battery by using the electrolyte of 0.05M-LiI-ether, and performing charge and discharge tests on the battery at room temperature according to a set charge and discharge program. The materials and operation were the same as in example 1 except that the electrolyte solution was different.
Fig. 1 is an SEM representation of lithium deposited on a copper foil after the first charge cycle of the full cell of example 2, and it can be seen that lithium particles deposited on the copper foil are large and mainly distributed in a block shape, and a little granular lithium is distributed on the lithium particles, indicating that under the shuttling effect of the electrolyte additive LiI, lithium deposition can be more uniform, and the generation of dead lithium can be reduced.
Fig. 2 is an SEM characterization of lithium deposition on the copper foil after the first discharge of the full cell of example 2, where the copper foil surface was flat with little remaining lithium, indicating that the shuttling of the electrolyte additive LiI activated dead lithium and reduced the buildup of dead lithium on the copper foil.
Example 3
And assembling the lithium-free cathode full battery by using the electrolyte solution and 0.025M-LiI-ester, and performing charge and discharge tests on the battery at room temperature according to the set charge and discharge program. The materials and operation were the same as in example 1 except that the electrolyte solution was different.
Example 4
And assembling the lithium-free cathode full cell by using the electrolyte 0.05M-LiI-ester, and carrying out charge and discharge tests on the cell at room temperature according to the set charge and discharge program. The materials and operation were the same as in example 1 except that the electrolyte solution was different.
Example 5
Using electrolyte solution of 0.025M-Li2S5Ether assembly of lithium-free negative electrode full cells, and charge and discharge tests were performed on the cells at room temperature according to the set charge and discharge program. The materials and operation were the same as in example 1 except that the electrolyte solution was different.
Example 6
Using an electrolyte of 0.05M-Li2S5Ether assembly of lithium-free negative electrode full cells, and charge and discharge tests were performed on the cells at room temperature according to the set charge and discharge program. The materials and operation were the same as in example 1 except that the electrolyte solution was different.
Comparative example 1
The lithium-free negative electrode full cell was assembled using a commercial ether electrolyte, and a charge and discharge test was performed on the cell at room temperature according to a set charge and discharge program. The materials and operation were the same as in example 1 except that the electrolyte solution was different.
Fig. 3 is an SEM representation of lithium deposited on the copper foil after the first charge of the full cell of comparative example 1, and it can be seen that most of the lithium on the copper foil is in powder form, possibly due to powdering of the deposited lithium metal, and that the powdered lithium particles are susceptible to losing electronic contact to form dead lithium and thus lose activity, in sharp contrast to fig. 1.
Fig. 4 is an SEM characterization of lithium deposited on the copper foil after the first discharge of the full cell of comparative example 1, and it can be seen that a large amount of rugged lithium metal is also present on the surface of the copper foil, in sharp contrast to fig. 2, indicating that lithium deposition on the copper foil in commercial ether electrolyte produces a large amount of dead lithium.
Comparative example 2
And (3) assembling the lithium-free cathode full battery by using the commercial ester electrolyte, and carrying out charge and discharge tests on the battery at room temperature according to the set charge and discharge program. The materials and operation were the same as in example 1 except that the electrolyte solution was different.
FIG. 5 is a comparison of the long cycle performance of examples 2, 5 and comparative example 1, and it can be seen that the LiI electrolyte additive used in example 2 is compared to the Li electrolyte additive used in example 52S5The electrolyte additive can effectively activate dead lithium by utilizing shuttle effect, thereby obviously improving the cycle performance of the lithium-free cathode full battery.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A lithium-free negative electrode-lithium secondary battery characterized in that:
the battery adopts modified electrolyte, trace substances are added in the modified electrolyte and can generate a shuttling effect, and the trace substances shuttle back and forth between a positive electrode and a negative electrode of the battery and generate electrochemical and chemical reactions to eliminate lithium dendrites and activate dead lithium; the trace substances and the intermediate products thereof can be dissolved in the electrolyte, and can respectively perform reduction reaction and oxidation reaction with the cathode and the anode in the working voltage interval of the battery, and finally return to the initial state.
2. The lithium-free negative electrode-lithium secondary battery according to claim 1, wherein: the trace substance comprises iodine, polyiodide, lithium iodide and lithium polysulfide.
3. The lithium-free negative electrode-lithium secondary battery according to claim 1, wherein: the lithium-free negative electrode of the battery is composed of a metallic current collector.
4. The lithium-free negative electrode-lithium secondary battery according to claim 3, wherein: the metal current collector is made of copper foil.
5. The lithium-free negative electrode-lithium secondary battery according to claim 1, wherein: the positive electrode of the battery is a lithium-containing positive electrode.
6. The lithium-free negative electrode-lithium secondary battery according to claim 5, wherein: the positive electrode comprises lithium iron phosphate, lithium cobaltate and nickel cobalt manganese lithium.
7. The lithium-free negative electrode-lithium secondary battery as claimed in any one of claims 1 to 6, wherein: the concentration of trace substances in the modified electrolyte is less than 0.5M.
8. The lithium-free negative electrode-lithium secondary battery according to claim 7, wherein: the concentration of the trace substance is less than 0.1M.
9. A method of manufacturing the lithium-free negative electrode-lithium secondary battery as claimed in any one of claims 1 to 8.
10. The method of preparing a lithium-free negative electrode-lithium secondary battery according to claim 9, wherein: adding trace substances into the electrolyte, and stirring the electrolyte on a magnetic stirring table at room temperature until the trace substances are completely dissolved to obtain the modified electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011067121.XA CN112331904A (en) | 2020-10-05 | 2020-10-05 | Lithium-free negative electrode-lithium secondary battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011067121.XA CN112331904A (en) | 2020-10-05 | 2020-10-05 | Lithium-free negative electrode-lithium secondary battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112331904A true CN112331904A (en) | 2021-02-05 |
Family
ID=74314553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011067121.XA Pending CN112331904A (en) | 2020-10-05 | 2020-10-05 | Lithium-free negative electrode-lithium secondary battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112331904A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113782815A (en) * | 2021-08-17 | 2021-12-10 | 浙江工业大学 | A kind of lithium ion battery and method of photo-assisted activation of dead lithium |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101501897A (en) * | 2006-08-10 | 2009-08-05 | 奥克斯能源有限公司 | A cell or battery with a metal lithium electrode and electrolytes therefor |
| CN102084523A (en) * | 2008-05-02 | 2011-06-01 | 奥克斯能源有限公司 | Rechargeable battery with negative lithium electrode |
| CN106471663A (en) * | 2014-06-27 | 2017-03-01 | 巴登-符腾堡州太阳能和氢能公益基金研究中心 | Controllable type electric discharge using the accumulator of oxidoreduction shuttle additive |
| KR20180025581A (en) * | 2016-09-01 | 2018-03-09 | 주식회사 엘지화학 | Electrolyte comprising lithium polysulfide for lithium air battery, and lithium air battery |
| CN109526240A (en) * | 2016-06-08 | 2019-03-26 | 固态能源系统有限责任公司 | High-energy density, high power density, high capacity and the rechargeable battery of feasible " no anode " at room temperature |
| CN110754009A (en) * | 2017-08-28 | 2020-02-04 | 株式会社Lg化学 | Lithium secondary battery |
| US10727545B1 (en) * | 2019-04-12 | 2020-07-28 | Ses Holdings Pte. Ltd. | Methods of charging secondary lithium metal batteries to reactive dead lithium with redox shuttling additives and battery control systems incorporating the same |
-
2020
- 2020-10-05 CN CN202011067121.XA patent/CN112331904A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101501897A (en) * | 2006-08-10 | 2009-08-05 | 奥克斯能源有限公司 | A cell or battery with a metal lithium electrode and electrolytes therefor |
| CN102084523A (en) * | 2008-05-02 | 2011-06-01 | 奥克斯能源有限公司 | Rechargeable battery with negative lithium electrode |
| CN106471663A (en) * | 2014-06-27 | 2017-03-01 | 巴登-符腾堡州太阳能和氢能公益基金研究中心 | Controllable type electric discharge using the accumulator of oxidoreduction shuttle additive |
| CN109526240A (en) * | 2016-06-08 | 2019-03-26 | 固态能源系统有限责任公司 | High-energy density, high power density, high capacity and the rechargeable battery of feasible " no anode " at room temperature |
| KR20180025581A (en) * | 2016-09-01 | 2018-03-09 | 주식회사 엘지화학 | Electrolyte comprising lithium polysulfide for lithium air battery, and lithium air battery |
| CN110754009A (en) * | 2017-08-28 | 2020-02-04 | 株式会社Lg化学 | Lithium secondary battery |
| US10727545B1 (en) * | 2019-04-12 | 2020-07-28 | Ses Holdings Pte. Ltd. | Methods of charging secondary lithium metal batteries to reactive dead lithium with redox shuttling additives and battery control systems incorporating the same |
Non-Patent Citations (2)
| Title |
|---|
| 宋天佑等: "《无机化学 下》", 31 December 2004, 高等教育出版社 * |
| 王文洁等: "《药物检测技术》", 31 January 2017, 中国医药科技出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113782815A (en) * | 2021-08-17 | 2021-12-10 | 浙江工业大学 | A kind of lithium ion battery and method of photo-assisted activation of dead lithium |
| CN113782815B (en) * | 2021-08-17 | 2023-03-14 | 浙江工业大学 | Lithium ion battery and method for activating dead lithium by light assistance |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110165218B (en) | Application of a positive sodium supplement in sodium ion batteries | |
| Zhao et al. | High-efficiency cathode potassium compensation and interfacial stability improvement enabled by dipotassium squarate for potassium-ion batteries | |
| CN113130896A (en) | Positive electrode material for sodium ion battery and sodium ion battery comprising same | |
| CN108539171B (en) | Preparation method of zinc sulfide and graphene oxide compound and application of compound in positive electrode material of lithium-sulfur battery | |
| Jin et al. | Stabilizing interfacial reactions for stable cycling of high‐voltage sodium batteries | |
| CN112490394B (en) | Chemical prelithiation method for graphite electrode of lithium ion battery | |
| CN105789553A (en) | Positive electrode of lithium ion battery | |
| CN108767263A (en) | A kind of preparation method and application of modified metal cathode of lithium copper foil current collector | |
| CN114203963A (en) | Carbon material lithium metal composite negative electrode and preparation method and application thereof | |
| CN112885985A (en) | Positive pole piece and preparation method thereof, electrochemical energy storage device and pre-metallization method of electrochemical energy storage device | |
| CN113299897A (en) | Na3V2(PO4)3Mixed ion full cell with @ C as anode material | |
| CN114566650A (en) | Sodium supplement additive and method for positive electrode of sodium ion battery, positive electrode and flexible electrode | |
| CN109802131A (en) | Lithium ion battery and its negative electrode tab and negative electrode material and preparation process | |
| CN108539188A (en) | A kind of preparation method of liquid metal nano-particle and the preparation method of lithium ion battery | |
| CN115312834A (en) | Potassium-based double-ion battery with double graphite electrodes and preparation method thereof | |
| CN113540413A (en) | Positive electrode material, positive plate, lithium ion battery and preparation method thereof | |
| CN107785559B (en) | Graphene-lithium titanate composite material, preparation method thereof, lithium-supplementing graphene-lithium titanate film and lithium battery | |
| CN109378220A (en) | A kind of high voltage mixed type lithium ion super capacitor and preparation method thereof | |
| CN114204009A (en) | Lithium ion battery anode lithium supplement additive and lithium ion battery comprising same | |
| CN112331904A (en) | Lithium-free negative electrode-lithium secondary battery and preparation method thereof | |
| CN113363490A (en) | Lithium secondary battery based on Li 2O-containing positive electrode and inactive material-free negative electrode and preparation method | |
| CN113659135B (en) | Application of iron sulfide in lithium iron phosphate secondary battery | |
| CN115579504A (en) | Lithium-sulfur battery based on lithium supplement technology and without lithium metal negative electrode and application thereof | |
| CN113346142A (en) | Low-concentration electrolyte for lithium ion secondary battery and lithium ion secondary battery | |
| CN218632196U (en) | Rechargeable 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210205 |