CN108011079A - A kind of surface modification method of lithium anode and application - Google Patents

A kind of surface modification method of lithium anode and application Download PDF

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Publication number
CN108011079A
CN108011079A CN201711084656.6A CN201711084656A CN108011079A CN 108011079 A CN108011079 A CN 108011079A CN 201711084656 A CN201711084656 A CN 201711084656A CN 108011079 A CN108011079 A CN 108011079A
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China
Prior art keywords
lithium
lithium anode
battery
modification method
surface modification
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CN201711084656.6A
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王丽平
李洁
李晶泽
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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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
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/134—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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A kind of surface modification method of lithium anode and application, belong to technical field of new energy material preparation.The present invention forms LiI and LiM alloy-layers by the way that lithium anode to be soaked to reaction in metal iodide solution, on surface, wherein, LiI is fast-ionic conductor, can effectively improve the ionic conductance of electrode and the performance of battery；And LiM alloy-layers component and volume during circulating battery will not change, lithium deposition occurs under alloy-layer, can effectively prevent the formation of Li dendrite, improve the security performance of battery, meanwhile, LiM alloy-layers can also provide the Li of stabilization for cell reaction+, and then improve the cycle performance of battery.

Description

A kind of surface modification method of lithium anode and application
Technical field
The invention belongs to technical field of new energy material preparation, and in particular to a kind of surface modification method of lithium anode And the application of the lithium anode after modification.
Background technology
Carbon material and Li4Ti5O12Material is common negative material in lithium ion battery, although being widely used, it is deposited Battery capacity room for promotion is too small the problems such as.And lithium metal light weight, price are low, specific capacity is high, can preferably meet existing The generation social demand for high energy density cells system.
Negative material of the lithium metal as lithium ion battery, it is maximum the problem of lithium can be being formed in battery charge and discharge process Dendrite, reduces the cycle efficieny and security feature of battery.At present, in order to suppress the formation of Li dendrite, the method for generally use It is to form inertia protective layer or generation solid electrolyte film in metallic lithium surface, however, the former easily takes off in cyclic process Fall, the latter and lithium metal interface stability are poor, can not meet the needs of practical application.Therefore, being badly in need of searching one kind can solve Certainly the problem of Li dendrite, and it can guarantee that the cycle characteristics of battery and the processing method of stability.
The content of the invention
The present invention for background technology there are the defects of, it is proposed that a kind of surface modification method of lithium anode and repair Application of the lithium metal in lithium ion battery after decorations.The method of the present invention is simply efficient, can effectively solve Li dendrite formation and The security risk brought, while also improve the cycle performance and energy density of battery.
Technical scheme is as follows：
A kind of surface modification method of lithium anode, comprises the following steps：
Step 1, add metal iodide in organic solvent, fully dissolving, obtain the concentration of metal iodide for 0.1~ The solution of 1mol/L；
Step 2, take lithium metal, after the oxide-film for removing its surface, is put into the metal iodide solution that step 1 obtains, After soaking 1~150s, clean, dry, the lithium anode after being modified.
Further, organic solvent described in step 1 for tetrahydrofuran, benzene, biphenyl, one kind in dimethyl sulfoxide (DMSO) or It is a variety of.
Further, metal iodide described in step 1 is magnesium iodide (MgI2), silver iodide (AlI3), boron iodide (BI3)、 Zinc iodide (ZnI2), indium iodide (InI3), gallium iodide (GaI3) in one or more.
Further, cleaned described in step 2, dry detailed process is：Table is cleaned using the organic solvent in step 1 Face, then naturally dry in an inert atmosphere.
Further, the lithium anode surface after modification described in step 2 forms the decorative layer that thickness is 10nm~1 μm.
A kind of lithium anode after being modified present invention also offers above method is in lithium-air battery, lithium-sulfur cell and lithium Application in ion battery.
Beneficial effects of the present invention are：
It is simple efficient the present invention provides a kind of surface modification method of lithium anode, it can effectively solve Li dendrite Formation and the security risk brought, while also improve the cycle performance and battery energy density of battery.The present invention pass through by Lithium anode soaks reaction in metal iodide, LiI and LiM alloy-layers are formed on surface, wherein, LiI is that fast ion is led Body, can effectively improve the ionic conductance of electrode and the performance of battery；And LiM alloy-layers component and body during circulating battery Product will not change, and lithium deposition occurs under alloy-layer, can effectively prevent the formation of Li dendrite, improve the safety of battery Performance, meanwhile, LiM alloy-layers can also provide the Li of stabilization for cell reaction+, and then improve the cycle performance of battery.
Brief description of the drawings
Fig. 1 is the performance test curve for the lithium-sulfur cell that the lithium anode after embodiment 1 is modified assembles；
Fig. 2 is the lithium ion battery that the lithium anode after present invention modification is assembled with unmodified lithium anode Performance test correlation curve.
Embodiment
With reference to the accompanying drawings and examples, technical scheme is described in detail.
A kind of surface modification method of lithium anode, specifically includes following steps：
Step 1, weigh metal iodide under inert gas atmosphere, then adds in organic solvent, fully dissolving, obtains Metal iodide solution；Wherein, the concentration of metal iodide is 0.1~1mol/L；
Step 2, take lithium metal, after the oxide-film for removing its surface, is put into the metal iodide solution that step 1 obtains, After soaking 1~150s, take out, cleaned using the organic solvent in step 1, and naturally dry in an inert atmosphere, obtain Lithium anode after modification.
Further, organic solvent described in step 1 for tetrahydrofuran, benzene, biphenyl, one kind in dimethyl sulfoxide (DMSO) or It is a variety of.
Further, metal iodide described in step 1 is magnesium iodide (MgI2), silver iodide (AlI3), boron iodide (BI3)、 Zinc iodide (ZnI2), indium iodide (InI3), gallium iodide (GaI3) in one or more.
Further, the use of metal iodide solution is organic during the organic solvent that uses is for step 1 when being cleaned in step 2 Solvent, is specially the one or more in tetrahydrofuran, benzene, biphenyl, dimethyl sulfoxide (DMSO).
Further, the lithium anode surface after modification described in step 2 forms the decorative layer that thickness is 10nm~1 μm.
A kind of lithium anode after being modified present invention also offers above method is in lithium-air battery, lithium-sulfur cell and lithium Application in ion battery.
Embodiment 1
A kind of surface modification method of lithium anode, specifically includes following steps：
Step 1, in Ar environment lower-weighing 0.407g AlI3Powder, then adds 10mL dimethyl sulfoxide (DMSO)s (DMSO) solution In, fully dissolving, obtains AlI3Concentration be 0.1mol/L AlI3/ DMSO solution；
Step 2, take lithium metal, after the oxide-film for removing its surface, is put into the AlI that step 1 obtains3In/DMSO solution, leaching After steeping 5s, take out, cleaned using dimethyl sulfoxide (DMSO) (DMSO), and the naturally dry under Ar compression rings border, the metal after being modified Cathode of lithium.
Using the lithium metal after modification as anode, lithium-sulfur cell is assembled.Fig. 1 is the lithium anode after embodiment 1 is modified Assemble the performance test curve of obtained lithium-sulfur cell；As shown in Figure 1, the lithium anode after embodiment 1 is modified assembles to obtain Lithium-sulfur cell, when current density is 100mA/g, discharge capacity is 1073mAh/g first for it, circulation 100 times after, capacity protect Hold as 798mAh/g, there is good battery energy density and cycle performance.
Embodiment 2
A kind of surface modification method of lithium anode, specifically includes following steps：
Step 1, in Ar environment lower-weighing 0.95g ZnI2Powder, then adds in 15mL tetrahydrofurans (THF), fully molten Solution, obtains ZnI2Concentration be 0.2mol/L ZnI2/ THF solution；
Step 2, take lithium metal, after the oxide-film for removing its surface, is put into the ZnI that step 1 obtains2In/THF solution, leaching After steeping 120s, take out, cleaned using tetrahydrofuran, and the naturally dry under Ar compression rings border, the lithium anode after being modified.
Embodiment 3
Difference lies in lithium metal is in ZnI in step 2 with embodiment 2 for embodiment 32Soaking time in/THF solution is 5s, remaining operation are same as Example 2.
Lithium metal after respectively modifying embodiment 2 and embodiment 3 is as anode, Li4Ti5O12Material is assembled as cathode Lithium ion battery；Then using unmodified lithium metal as anode, Li4Ti5O12Material assembles lithium ion battery as cathode, makees For contrast.Fig. 2 is the lithium that the lithium metal after embodiment 2 (immersion 2 minutes) and embodiment 3 (immersion 5s) modification is assembled as anode The performance test contrast for the lithium ion battery that ion battery is assembled with unmodified lithium metal (untreated samples) as anode is bent Line.As shown in Figure 2, when current density is 1A/g, the battery of the lithium metal assembling after the immersion of embodiment 3 5s, first electric discharge is held Measure as 161mAh/g, after circulation 2000 weeks, its capacity remains 155mAh/g；And embodiment 2 soak 2 minutes after lithium metal The battery of assembling, discharge capacity is 160mAh/g first, and after circulating 2000 weeks, its capacity is still maintained as 148mAh/g；However, The battery assembled without the lithium metal of moditied processing, discharge capacity is 162mAh/g first, after circulating 1000 weeks, its capacity drop As low as 113mAh/g.

Claims (6)

1. a kind of surface modification method of lithium anode, comprises the following steps：
Step 1, add metal iodide in organic solvent, fully dissolving, obtain the concentration of metal iodide for 0.1~ The solution of 1mol/L；
Step 2, take lithium metal, after the oxide-film for removing its surface, is put into the metal iodide solution that step 1 obtains, immersion 1 After~150s, clean, dry, the lithium anode after being modified.
2. the surface modification method of lithium anode according to claim 1, it is characterised in that organic described in step 1 Solvent is tetrahydrofuran, the one or more in benzene, biphenyl, dimethyl sulfoxide (DMSO).
3. the surface modification method of lithium anode according to claim 1, it is characterised in that metal described in step 1 Iodide are MgI2、AlI3、BI3、ZnI2、InI3、GaI3In one or more.
4. the surface modification method of lithium anode according to claim 1, it is characterised in that cleaning described in step 2, Dry detailed process is：Surface is cleaned using the organic solvent in step 1, then naturally dry in an inert atmosphere.
5. the surface modification method of lithium anode according to claim 1, it is characterised in that after modification described in step 2 Lithium anode surface formed thickness be 10nm~1 μm decorative layer.
6. the lithium anode after method modification any one of claim 1 to 5 is in lithium-air battery, lithium-sulfur cell and lithium Application in ion battery.
CN201711084656.6A 2017-11-07 2017-11-07 A kind of surface modification method of lithium anode and application Pending CN108011079A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109326771A (en) * 2018-11-20 2019-02-12 中国电力科学研究院有限公司 A kind of preparation method and ferric phosphate lithium cell of lithium anode
CN109585947A (en) * 2018-12-04 2019-04-05 安徽盟维新能源科技有限公司 A kind of lithium an- ode double protection method and application
CN110071284A (en) * 2019-03-01 2019-07-30 上海大学 The guard method of metal lithium electrode
CN110137435A (en) * 2019-05-13 2019-08-16 天津大学 Magnesium metal cathode preparation method containing fast ionic transport interface
CN111224068A (en) * 2018-11-27 2020-06-02 中国科学院大连化学物理研究所 Metal lithium cathode for lithium battery and lithium battery
CN111463405A (en) * 2020-04-08 2020-07-28 苏州清陶新能源科技有限公司 Method for polishing lithium metal and application thereof
CN112768695A (en) * 2021-01-13 2021-05-07 山东大学 High-safety dendrite-free lithium metal battery and preparation method and application thereof
CN112786885A (en) * 2021-01-06 2021-05-11 山东大学 Long-life and dendrite-free metal lithium negative electrode for lithium battery and preparation method and application thereof
CN112803026A (en) * 2021-02-01 2021-05-14 山东大学 Lithium negative electrode for dendrite-free all-solid-state battery and preparation method and application thereof
CN113193174A (en) * 2021-04-28 2021-07-30 昆山宝创新能源科技有限公司 Interface pretreatment liquid for silica prelithiation negative electrode and preparation method and application thereof
CN113363427A (en) * 2021-06-07 2021-09-07 中南大学 Preparation method of lithium alloy cathode for sulfide all-solid-state battery and battery thereof
CN115101855A (en) * 2022-06-23 2022-09-23 江汉大学 Lithium-air battery metal iodide additive and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102881862A (en) * 2011-07-12 2013-01-16 中国科学院上海硅酸盐研究所 Protective metal anode structure and preparation method thereof
CN106099091A (en) * 2016-08-29 2016-11-09 电子科技大学 A kind of lithium anode material of surface modification and preparation method thereof
CN106784636A (en) * 2016-12-29 2017-05-31 中国电子科技集团公司第十八研究所 Method for treating surface of metal lithium by using iodine solution and application of method in solid-state battery
CN106784629A (en) * 2017-01-19 2017-05-31 武汉大学 A kind of lithium metal battery cathode interface method of modifying

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102881862A (en) * 2011-07-12 2013-01-16 中国科学院上海硅酸盐研究所 Protective metal anode structure and preparation method thereof
CN106099091A (en) * 2016-08-29 2016-11-09 电子科技大学 A kind of lithium anode material of surface modification and preparation method thereof
CN106784636A (en) * 2016-12-29 2017-05-31 中国电子科技集团公司第十八研究所 Method for treating surface of metal lithium by using iodine solution and application of method in solid-state battery
CN106784629A (en) * 2017-01-19 2017-05-31 武汉大学 A kind of lithium metal battery cathode interface method of modifying

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MASASHI ISHIKAWA 等: "Pretreatment of Li metal anode with electrolyte additive for enhancing Li cycleability", 《JOURNAL OF POWER SOURCES》 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109326771B (en) * 2018-11-20 2022-03-11 中国电力科学研究院有限公司 Preparation method of metal lithium cathode and lithium iron phosphate battery
CN109326771A (en) * 2018-11-20 2019-02-12 中国电力科学研究院有限公司 A kind of preparation method and ferric phosphate lithium cell of lithium anode
CN111224068A (en) * 2018-11-27 2020-06-02 中国科学院大连化学物理研究所 Metal lithium cathode for lithium battery and lithium battery
CN109585947A (en) * 2018-12-04 2019-04-05 安徽盟维新能源科技有限公司 A kind of lithium an- ode double protection method and application
CN110071284A (en) * 2019-03-01 2019-07-30 上海大学 The guard method of metal lithium electrode
CN110071284B (en) * 2019-03-01 2022-06-14 上海大学 Method for protecting lithium metal electrode
CN110137435A (en) * 2019-05-13 2019-08-16 天津大学 Magnesium metal cathode preparation method containing fast ionic transport interface
CN111463405A (en) * 2020-04-08 2020-07-28 苏州清陶新能源科技有限公司 Method for polishing lithium metal and application thereof
CN111463405B (en) * 2020-04-08 2022-04-29 苏州清陶新能源科技有限公司 Method for polishing lithium metal and application thereof
CN112786885A (en) * 2021-01-06 2021-05-11 山东大学 Long-life and dendrite-free metal lithium negative electrode for lithium battery and preparation method and application thereof
CN112768695A (en) * 2021-01-13 2021-05-07 山东大学 High-safety dendrite-free lithium metal battery and preparation method and application thereof
CN112803026A (en) * 2021-02-01 2021-05-14 山东大学 Lithium negative electrode for dendrite-free all-solid-state battery and preparation method and application thereof
CN113193174A (en) * 2021-04-28 2021-07-30 昆山宝创新能源科技有限公司 Interface pretreatment liquid for silica prelithiation negative electrode and preparation method and application thereof
CN113363427A (en) * 2021-06-07 2021-09-07 中南大学 Preparation method of lithium alloy cathode for sulfide all-solid-state battery and battery thereof
CN115101855A (en) * 2022-06-23 2022-09-23 江汉大学 Lithium-air battery metal iodide additive and application thereof

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Application publication date: 20180508