CN106025187A - Method for preparing lithium anode for secondary battery - Google Patents

Method for preparing lithium anode for secondary battery Download PDF

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Publication number
CN106025187A
CN106025187A CN201610566937.4A CN201610566937A CN106025187A CN 106025187 A CN106025187 A CN 106025187A CN 201610566937 A CN201610566937 A CN 201610566937A CN 106025187 A CN106025187 A CN 106025187A
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China
Prior art keywords
deposition
metal
conductive substrates
template
preparation
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CN201610566937.4A
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Chinese (zh)
Inventor
洪波
赖延清
谢科予
刘晋
张治安
洪树
张凯
方静
李劼
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SHENZHEN RESEARCH INSTITUTE CENTRAL SOUTH UNIVERSITY
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SHENZHEN RESEARCH INSTITUTE CENTRAL SOUTH UNIVERSITY
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Priority to CN201610566937.4A priority Critical patent/CN106025187A/en
Publication of CN106025187A publication Critical patent/CN106025187A/en
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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
    • 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

Abstract

The invention discloses a method for preparing a lithium anode for a secondary battery. The method comprises the following steps: first, obtaining electronic insulator nanotubes growing on a conductive substrate according to any one of a template method, an electrospinning method and an anodic oxidation method; depositing Li in the nanotubes according to any one of electrodeposition, vapor deposition, mechanical squeezing, atomic layer deposition, magnetron sputtering, and spray deposition, so that a lithium-rich nanotube anode composed of the conductive substrate, the nanotubes growing on the conductive substrate, and lithium metal exists in the nanotubes is formed. The lithium-rich nanotube anode prepared according to the method has the advantages of high volumetric energy, no dendrite, high charge-discharge coulombic efficiency and long cycle life; the method has a simple technological process and is convenient for industrial production.

Description

A kind of preparation method of secondary cell lithium anode
Technical field
The invention belongs to energy storage device field, be specifically related to the preparation method of a kind of secondary cell lithium anodes.
Background technology
Lithium Li is minimum (atomic radius 0.76), the lightest (density 0.53g/cm3) and the minimum (-3.040V vs. of current potential SHE) metallic element, the secondary cell with metal Li as anode has high energy density, is described as battery design manufacture " Holy grail " of industry, once there is the research and development upsurge of lithium metal secondary battery in the 1970's to 1980.But, the lithium of metallic Li anode Dendritic growth and the battery life caused short with poor safety performance etc. problem, seriously constrain sending out of metal Li secondary cell Exhibition, although period Moli energy company once released metal Li secondary cell product, but the fire accident occurred for 1989 is led Cause the development of metal Li secondary cell and be absorbed in pause.
Lithium dendrite growth is the fundamental issue hindering lithium metal anode commercial applications in the secondary battery, thus will Cause following three aspect problems: (1) Li dendrite repeatedly grows and dissolves so that it is surface SEI film is constantly formed, peels off and piles up, Causing battery efficiency to be difficult to improve, interface impedance persistently increases, and finally causes battery failure；(2) during battery discharge, lithium Preferentially there is the dendrite root in easily electric discharge in anodic solution, the molten dendrite having no progeny of root will attach to can not the SEI of electronic conduction On film, become " dead lithium ", cause electrode active material to lose, make battery capacity decay, thus shorten battery life；(3) lithium branch Brilliant undue growth may pierce through barrier film and even extend to positive pole, causes internal short-circuit of battery, causes battery catches fire even to explode, Bring great potential safety hazard.
Due to lithium dendrite growth feature and the complexity of lithium anodes working environment, the equal nothing of all kinds of methods proposed at present Method persistently efficiently solves lithium dendrite growth problem.
Summary of the invention
The problem that all cannot persistently efficiently solve lithium dendrite growth for existing secondary cell lithium anode preparation method, It is desirable to provide propose the preparation method of a kind of secondary cell lithium anode, the lithium anode being prepared by the method for the present invention exists While solving the problem that coulombic efficiency is low, cycle life is short, can the most effectively solve the lithium branch that secondary cell lithium anode exists The problem of crystals growth.
For reaching goal of the invention, the technical solution used in the present invention is: the preparation of a kind of secondary cell lithium anodes Method, in metal, alloy or Carbon Materials conductive substrates, any one by template, method of electrostatic spinning, anodizing The method of kind, it is thus achieved that the metal oxide nanotubes of the insulation being grown in conductive substrates, described metal oxide nanotubes is TiO2、CuO、Fe2O3、Al2O3、ZrO2、SiO2、MoO3、HfO2、Nb2O5、WO3、Ta2O5Any one in nanotube；Then lead to Cross any one method in electro-deposition, vapour deposition, mechanical presses, ald, magnetron sputtering, jet deposition, by gold Belong to Li to fill to the pipeline of metal oxide nanotubes, thus obtain secondary cell lithium anode.
Preferred as the present invention, described metal or alloy conductive substrates is in Cu, Sn, Tn, Sb, Al, Mg, Pt, Ag, Au Any one or more combination formed alloy.Described Carbon Materials conductive substrates is graphite, activated carbon, Graphene, acetylene black, carbon Any one or more combination in nanotube.
Preferred as the present invention, described metal oxide nanotubes height is 100nm-1mm, manages a diameter of 10nm- 100nm。
Specifically, the concretely comprising the following steps of method of electrostatic spinning: by polyacrylonitrile, dimethylformamide, polyvinylpyrrolidone Mix homogeneously, after solution is clarified completely, insulation continuous stirring, prepare spinning liquid；The spinning liquid of preparation is introduced Static Spinning Silk device is formed in conductive substrates polymer nanofiber array；Sunk by electrochemical deposition, magnetron sputtering, chemical gaseous phase Any one method during long-pending, ald, heat are deposited with is thin at polymer nanofiber array surface one layer of oxide of deposition Film；There is the polymer fiber of sull to carry out high temperature sintering by obtaining surface deposition, remove polymer fiber, can obtain The oxidate nano tubular construction being grown in conductive substrates.
Specifically, the concretely comprising the following steps of described anodizing: deposited by electro-deposition, magnetron sputtering, chemical gaseous phase, Any one method pre-deposition layer of metal thin film in conductive substrates in heat evaporation, ald；Described metallic film For any one in Ti, Al, Fe, Zr, Cu, Mo, thickness of metal film is 100nm-1mm；The metallic film obtained is placed in Alkalescence or acidic electrolysis bath are obtained the metal oxide nanotubes structure being grown in conductive substrates by anodic oxidation.Described Acidic electrolysis bath is acid flux material and water or the combination of organic solvent.Described acid flux material is HF, HNO3、HCl、HClO4、 H2CrO7、H2SO4, (NH4) H2PO4、NH4F、H3PO4, (NH4)2SO4, (NH4)2TiF6, the group of one or more in NaF, KF Close.Described organic solvent is glycerol, ethylene glycol, glycerol, ethylene glycol, N, any one in N-dimethylformamide.
As preferably, being contained in pre-deposition layer of metal thin film in conductive substrates, thickness of metal film is preferably 100nm- 1mm。
Specifically, described template concretely comprises the following steps: with the Al being grown in conductive substrates2O3、SiO2, ZnO nanotube/ Any one in array is template；By electrochemical deposition, magnetron sputtering, chemical gaseous phase deposition, ald, heat evaporation In any one method nano-tube array template surface deposit layer of metal thin film；Described metallic film is Ti, Al, Fe, Any one in Zr, Cu, Mo, Hf, Nb, W, Ta；In NaOH solution, dissolve nanometer stick array, and aoxidize in oxygen-containing atmosphere Sintering processes i.e. can obtain the metal oxide nanotubes structure being grown in conductive substrates.
As preferably, when nano-tube array template surface deposition metallic film, thickness of metal film is preferably 100nm- 1mm。
In the present invention, the nanotube being grown in conductive substrates can also is that polymer nanotube, if polymer nano Mitron, then be suitable for template.Specifically, the rich lighium polymer nanotube lithium anode of this secondary cell is prepared by template Concrete preparation method be: in metal, alloy or Carbon Materials conductive substrates, with the Al being grown in conductive substrates2O3、SiO2、 Any one in ZnO nanotube/array is template, polymer is heated to fusing and drops in nanometer rods template, treating that melt is complete After being entirely impregnated with template, remove oxide nano template by the NaOH aqueous solution soaking of 3M and i.e. obtain polymer nanotube；Then By any one method in electro-deposition, vapour deposition, mechanical presses, ald, magnetron sputtering, jet deposition, will Metal Li fills to the pipeline belonging to oxide nano, thus obtains secondary cell lithium anode.Equally, described metal or conjunction Gold conductive substrates is the alloy that any one or more combination in Cu, Sn, Tn, Sb, Al, Mg, Pt, Ag, Au is formed.Described raw material of wood-charcoal Material conductive substrates is any one or more combination in graphite, activated carbon, Graphene, acetylene black, CNT.
Described polymer is polypropylene (PP), polystyrene (PS), Kynoar (PVDF), politef (PTFE), polymethyl-benzene e pioic acid methyl ester (PMMA), polypara-phenylene vinylene (PPV), Merlon (PC), polylactic acid (PLA), poly- Any one in vinyl chloride (PVC), ABS, nylon (PA).
The preparation method of the secondary cell lithium anode of the present invention forms the nanotubes of electronic isolation in conductive substrates Structure, this nanotubes oriented growth is in conductive substrates, then lithium metal is filled into the nanotubes structure of electronic isolation In, thus limit Li lateral growth, it is unidirectional growth/dissolving that in battery charge and discharge process Li is effectively ensured, and is solving coulomb effect While the problem that rate is low, cycle life is short, lithium dendrite growth can be prevented effectively from, thus solve puzzlement secondary cell lithium anode The problem that present in technology, Li dendrite is many, thus ensure the stability of cyclic process electrode structure, it is thus achieved that high specific energy, without branch Coulombic efficiency brilliant, high and long circulation life and the high lithium anodes of security performance.
The rich lithium nanotube anode prepared by method that the present invention proposes has high energy density per unit volume, without dendrite, high charge and discharge Electricity coulombic efficiency and long circulation life spy's advantage, and the preparation method of the present invention has, and technological process is simple, be easy to industry metaplasia The advantages such as product.The present invention is expected to fundamentally to solve to perplex lithium metal secondary battery many Li dendrites for many years and low coulombic efficiency etc. Key scientific problems, thus advance the high-energy secondary battery commercial applications such as lithium ion battery, lithium sulfur, lithium air.
Detailed description of the invention
The following is illustrating of presently preferred embodiments of the present invention, the present invention is not constituted any restriction, the i.e. present invention Being not meant to be only limitted to above-described embodiment, the most common modification or alternative compounds are all contained in the application power In profit requires limited range.
Embodiment 1
With copper as conductive substrates, at one layer of Ti of electro-deposition at the bottom of cuprio, then at 1%HF+0.5%NH4F+H2O mixed solution passes through Anodic oxidation forms Cu base TiO2Nanotube, tube diameters is about 10nm, and height is 100nm.Glove box is sunk by electricity Amass Li orientated deposition in Cu base TiO2In nanotube, prepare rich lithium TiO2Nanotube anode (Cu/Li-TiO2).
Embodiment 2
At one layer of Fe of electro-deposition at the bottom of cuprio, at 1%HF+0.5%NH4F+0.2%HNO3+ glycerol electrolyte passes through anodic oxidation Form Cu base Fe2O3Nanotube, tube diameters is about 100nm, and height is 10um.By mechanical presses mode in glove box Li is pressed in base Fe2O3In nanotube, prepare rich lithium Fe2O3Nanotube anode (Cu/Li-Fe2O3).
Embodiment 3
By polyacrylonitrile, dimethylformamide, polyvinylpyrrolidone mix homogeneously, after solution is clarified completely, insulation is the most continuous Stirring, prepares spinning liquid；The spinning liquid of preparation is introduced in electrostatic spinning apparatus in graphite base, obtain polymer nanocomposite fibre Dimension array；One layer of SiO is deposited in polymer nanofiber array surface by ald2Thin film；Surface deposition will be obtained There is SiO2The polymer fiber of thin film is sintered at 800 DEG C, removes polymer fiber, can obtain and be grown on conductive substrates On SiO2Nano tube structure.Tube diameters is about 500nm, and height is 1mm.Li is oriented by glove box by electro-deposition It is deposited on graphite-based SiO2In nanotube, prepare rich lithium SiO2Nanotube anode (graphite/Li-SiO2).
Embodiment 4
To be grown on the suprabasil Al of Cu2O3Nanometer stick array is template；By magnetron sputtering at nanometer stick array template surface Deposit one layer of Zr metallic film；In NaOH solution, dissolve nanometer stick array, and oxidation and sinter processes in oxygen-containing atmosphere Obtain the Cu base ZrO being grown in conductive substrates2Nano tube structure.Tube diameters is about 100nm, and height is 100nm.Very Li is deposited on ZrO by heat evaporation mode by Altitude2In nanotube, prepare rich lithium ZrO2Nanotube anode (Cu/Li- ZrO2).
Embodiment 5
With copper as conductive substrates, at one layer of Al of magnetron sputtering at the bottom of cuprio, then form Al by anodic oxidation2O3Nanotube, To cuprio Al2O3Nanotube template, is then heated to PP granule fusing and drops in cuprio Al2O3Nanotube template, treats that melt is complete After being entirely impregnated with template, obtain cuprio PP nano-tube array by the NaOH aqueous solution soaking of 3M.Mechanical presses is passed through in glove box Li is pressed in based nanotube array by mode, prepares oriented growth/dissolving lithium anode (Cu/Li-PP).
Performance test
High voltage cycle performance test, concrete grammar is carried out after the oriented growth that the present invention prepares/dissolving lithium anode assembling battery As follows with test result:
1. the assembling of battery: with the load S CNT in coating and aluminium foil as positive pole, 0.8M LiTFI(DOL:DME=1:1) be Electrolyte, the oriented growth/dissolving lithium anode unit prepared with the present invention dresses up 2032 button lithium-sulfur cells, barrier film employing Celgard2400, battery standing was tested after 12 hours.
2. cycle performance of battery test: room temperature 25 ± 5 DEG C, under conditions of relative humidity 50 ~ 80%, battery is carried out 1.8-2.6 V cycle performance of battery is tested, and testing procedure is: a. 0.5C constant-current charge is to 2.6 V, and then constant-voltage charge is to cutting Only electric current 0.01 C；Stand 5 minutes；B. 0.5C constant-current discharge is to 1.8 V, stands 5 minutes；C. circulation step a and b, circulation Number of times is 100 times.
The battery testing correlated results that embodiment 1-5 prepares sees attached list 1.
Subordinate list 1
Knowable to subordinate list 1 battery performance test data, use the lithium-sulfur cell of embodiment of the present invention 1-5 lithium anodes 100 Capability retention after secondary circulation is near or above 85%, far above tradition lithium sheet anode.

Claims (8)

1. the preparation method of a secondary cell lithium anode, it is characterised in that its step is followed successively by: (1) metal, alloy or In Carbon Materials conductive substrates, by any one method in template, method of electrostatic spinning, anodizing, it is thus achieved that be grown on The metal oxide nanotubes of the electronic isolation in conductive substrates；Described metal oxide nanotubes is TiO2、CuO、Fe2O3、 Al2O3、ZrO2、SiO2、MoO3、HfO2、Nb2O5、WO3、Ta2O5In any one；(2) then by electro-deposition, vapour deposition, Any one method in mechanical presses, ald, magnetron sputtering, jet deposition, fills metal Li to burning In the pipeline of thing nanotube, thus obtain secondary cell lithium anode；Described metal or alloy conductive substrates is Cu, Sn, Tn, The alloy that any one or more combination in Sb, Al, Mg, Pt, Ag, Au is formed；Described Carbon Materials conductive substrates is graphite, activity Any one or more combination in charcoal, Graphene, acetylene black, CNT.
Preparation method the most according to claim 1, it is characterised in that: concretely comprising the following steps of described method of electrostatic spinning, will be poly- Acrylonitrile, dimethylformamide, polyvinylpyrrolidone mix homogeneously, after solution is clarified completely, insulation continuous stirring, preparation Spinning liquid；The spinning liquid of preparation is introduced in electrostatic spinning apparatus in conductive substrates, form polymer nanofiber array；Logical Any one method in electrochemical deposition, magnetron sputtering, chemical gaseous phase deposition, ald, heat evaporation of crossing is at polymer Nanofiber array surface deposition layer of metal sull；The polymer of metal-oxide film is had by obtaining surface deposition Fiber carries out high temperature sintering, removes polymer fiber, can obtain the metal oxide nanotubes being grown in conductive substrates.
Preparation method the most according to claim 1, it is characterised in that: concretely comprising the following steps of described anodizing, pass through Any one method in electro-deposition, magnetron sputtering, chemical gaseous phase deposition, heat evaporation, ald is pre-in conductive substrates Deposition layer of metal thin film；Described metallic film is any one in Ti, Al, Fe, Zr, Cu, Mo；The metallic film that will obtain It is placed in alkalescence or acidic electrolysis bath and obtains, by anodic oxidation, the metal oxide nanotubes that is grown in conductive substrates；Described Acidic electrolysis bath is acid flux material and water or the combination of organic solvent, and described acid flux material is HF, HNO3、HCl、HClO4、 H2CrO7、H2SO4, (NH4) H2PO4、NH4F、H3PO4, (NH4)2SO4, (NH4)2TiF6, the group of one or more in NaF, KF Close；Described organic solvent is glycerol, ethylene glycol, glycerol, ethylene glycol, N, any one in N-dimethylformamide.
Preparation method the most according to claim 3, it is characterised in that: pre-deposition layer of metal thin film in conductive substrates Time, thickness of metal film is 100nm-1mm.
Preparation method the most according to claim 1, it is characterised in that: described template concretely comprises the following steps, and leads to be grown on The suprabasil Al of electricity2O3、SiO2, any one in ZnO nanotube/array be template；By electrochemical deposition, magnetron sputtering, Any one method in chemical gaseous phase deposition, ald, heat evaporation deposits one layer of gold at nano-tube array template surface Belong to thin film；Described metallic film is any one in Ti, Al, Fe, Zr, Cu, Mo, Hf, Nb, W, Ta, and thickness of metal film is 100nm-1mm；In NaOH solution, dissolve nanometer stick array, and oxidation and sinter process i.e. can be grown in oxygen-containing atmosphere Metal oxide nanotubes in conductive substrates.
Preparation method the most according to claim 5, it is characterised in that: sink at the nano-tube array template surface as template During long-pending layer of metal thin film, thickness of metal film is 100nm-1mm.
7. according to the preparation method one of described in claim 1 ~ 6, it is characterised in that: described metal oxide nanotubes height is 100nm-1mm, a diameter of 10nm-100nm.
8. the preparation method of a secondary cell lithium anodes, it is characterised in that its step is followed successively by: (1) is in metal, conjunction On gold or Carbon Materials conductive substrates, with the Al being grown in conductive substrates2O3、SiO2, any one in ZnO nano-rod array For template, polymer being heated to fusing and drops in nanometer rods template, described polymer is polypropylene, polystyrene, gathers partially Fluorothene, politef, polymethyl-benzene e pioic acid methyl ester, polypara-phenylene vinylene, Merlon, polylactic acid, polrvinyl chloride, Any one in ABS, nylon；Described metal or alloy conductive substrates is appointing in Cu, Sn, Tn, Sb, Al, Mg, Pt, Ag, Au The alloy that one or more combinations are formed；Described Carbon Materials conductive substrates is graphite, activated carbon, Graphene, acetylene black, carbon nanometer Any one or more combination in pipe；(2) after melt is impregnated with template completely, burning is removed by NaOH aqueous solution soaking Thing nanotube template, i.e. obtains polymer nanotube；(3) then by electro-deposition, vapour deposition, mechanical presses, atomic layer deposition Any one method in long-pending, magnetron sputtering, jet deposition, fills metal Li to the pipeline of polymer nanotube, thus Obtain secondary cell lithium anode.
CN201610566937.4A 2016-07-17 2016-07-17 Method for preparing lithium anode for secondary battery Pending CN106025187A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108539153A (en) * 2018-03-27 2018-09-14 电子科技大学 Lithium metal composite negative pole material and preparation method thereof
CN112490411A (en) * 2020-11-25 2021-03-12 哈尔滨工业大学 Method for protecting lithium metal negative electrode through in-situ film forming

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108539153A (en) * 2018-03-27 2018-09-14 电子科技大学 Lithium metal composite negative pole material and preparation method thereof
CN112490411A (en) * 2020-11-25 2021-03-12 哈尔滨工业大学 Method for protecting lithium metal negative electrode through in-situ film forming

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Application publication date: 20161012