CN106654160A - Electrode plate activation method for negative electrode based on passivation metal lithium powder - Google Patents
Electrode plate activation method for negative electrode based on passivation metal lithium powder Download PDFInfo
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- CN106654160A CN106654160A CN201710054465.9A CN201710054465A CN106654160A CN 106654160 A CN106654160 A CN 106654160A CN 201710054465 A CN201710054465 A CN 201710054465A CN 106654160 A CN106654160 A CN 106654160A
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- Prior art keywords
- lithium powder
- electrode plate
- metal lithium
- graphite
- activation method
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- 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
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- 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)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an electrode plate activation method for a negative electrode based on passivation metal lithium powder. The electrode plate activation method comprises the following steps of uniformly coating a graphite electrode plate, which takes a copper sheet as a current collector, with a metal lithium powder-containing butadiene styrene rubber/methylbenzene solution through a coating machine to obtain a metal lithium powder/graphite/copper electrode plate; transferring the electrode plate to a glove box under protection of argon, and drying; performing rolling and activating on the dried electrode plate in the glove box under protection of argon by adopting a roller press; and preserving the rolled and activated electrode plate in the glove box under protection of argon for use. According to the electrode plate activation method, the rolling pressure loaded on the electrode plate is controlled through the roller press, the passivation layer-containing metal lithium powder is smashed through mechanical external force, and more metal lithium surfaces can be exposed, so that the electrochemical activity of the metal lithium powder can be improved, and the metal lithium powder-based lithium ion battery performance can be improved; and the electrode plate activation method has the characteristics of simple and environment friendly process, capability of realizing large-scale production easily, super-high electrochemical capacity per gram and the like.
Description
Technical field
The present invention relates to electrochemical material manufacturing technology field, and in particular to a kind of electricity based on passive metal lithium powder negative pole
Pole piece activation method.
Background technology
Because lithium ion battery has energy density high, lightweight and the features such as life-span length so as to face on the mobile apparatus
It is very popular as power supply.Sony is first commercialized lithium ion battery within 1991, and from this global range is opened
The research boom of interior lithium ion battery material.But, for the energy density of lithium ion battery itself, the size of its capacity with
Electrode material species is closely related.The electrode material of exploitation high power capacity is always the core of lithium ion battery worker in global range
One of heart work.Graphite is the negative material for being currently widely used in lithium ion battery, but because it only has the reason of 372mAh/g
By capacity, so as to constrain the energy density of battery.Lithium anode material has very tempting application prospect, because its reason
3650mAh/g is reached by capacity density, is 10 times of conventional graphite electrodes theoretical capacity, be the lithium ion for setting up high-energy-density
One of optimal candidate materials of battery system.
During li-ion electrode materials are applied to collector, traditional method be using PVDF (Kynoar) with
It is higher that NMP (1-METHYLPYRROLIDONE/oiliness) or CMC (sodium carboxymethylcellulose) is mixed to get viscosity with water (water solubility)
Solution, and active material is evenly spread in above-mentioned solution, and it is carried out on a current collector even spread.And in body series
In, as binding agent, metallic lithium powder is dispersed therein with butadiene-styrene rubber (the SBR)/toluene solution that mass fraction is 2%, obtain
Uniform lithium metal particle/SBR/ toluene solutions, then coater (or spraying process) is by lithium metal particle/SBR/ toluene
Solution evenly spreads to negative pole copper current collector (or scribbling the copper current collector of graphite linings) surface, and is dried removal toluene, obtains
Obtain the good lithium metal mosaic electrode piece of homogeneity.The achievable lithium metal particle of this strategy on a current collector dispersed,
Method is simple, is especially advantageous for extensive industrialization operation.
But, there is one layer of passivation due to the generation of side reaction in the metallic lithium powder surface produced by organic silicone oil
Layer, its Main Ingredients and Appearance is lithium carbonate, lithia etc..The presence of the passivation layer, can hinder lithium metal lithium ion in the electrolytic solution
Abjection, and increase the internal resistance of cell.Therefore, metallic lithium powder outer passivation layer activated have very much must by rational method
Will.
The content of the invention
It is an object of the invention to provide a kind of electrode slice activation method based on passive metal lithium powder negative pole, using roll squeezer
Rolling pressure of the controlled loading on electrode slice, the metallic lithium powder containing passivation layer is crushed by mechanical external force, is allowed more
Many metallic lithium surfaces come out, and so as to increase the electro-chemical activity of metallic lithium powder, improve based on the lithium ion of metallic lithium powder
Battery performance, with process is simple environmental protection, is easy to amplify the features such as metaplasia is produced, product has the electrochemistry gram volume of superelevation.
To achieve these goals, the technical solution used in the present invention is as follows：
A kind of electrode slice activation method based on passive metal lithium powder negative pole, comprises the steps：
1) adopt coating machine to be uniformly coated to the butadiene-styrene rubber containing metallic lithium powder (SBR)/toluene solution to be with copper sheet
On the graphite electrode piece of collector, metallic lithium powder/graphite/copper electrode piece is obtained；
2) metallic lithium powder/graphite/copper electrode piece is transferred to the glove box of argon gas protection, is dried, it is standby；
3) dried metallic lithium powder/graphite/copper electrode piece is carried out in the glove box that argon gas is protected using roll squeezer
Roll-in, controls roll squeezer roll gap size, allows metallic lithium powder/graphite/copper electrode piece at the uniform velocity to carry out roll-in activation by roll gap；
4) metallic lithium powder/graphite/copper electrode piece after roll-in is activated is stored in standby in the glove box of argon gas protection.
According to above scheme, the mass concentration of butadiene-styrene rubber is 2% in the butadiene-styrene rubber/toluene solution.
According to above scheme, the temperature in glove box when being dried is 60 DEG C, and drying time is 4h.
According to above scheme, roll squeezer roll gap size is controlled when the roll-in is activated, allow metallic lithium powder/graphite/copper electrode
Piece at the uniform velocity passes through roll squeezer roll gap.
The invention has the beneficial effects as follows：
1) present invention is binding agent using the SBR/ toluene solutions that mass concentration stable in properties is 2%, by lithium metal
Grain is distributed in its suspension and carries out even spread, by the rolling pressure using roll squeezer controlled loading on electrode slice,
Metallic lithium powder containing passivation layer is crushed by mechanical external force, allows more metallic lithium surfaces to come out, so as to increase
Plus the electro-chemical activity of metallic lithium powder, the lithium metal particle contained on electrode slice is used as lithium ion battery or other electrochemical devices
Reversible Cycle lithium source, the electrochemistry gram volume with superelevation；
2) present invention with process is simple environmental protection, be easy to amplify that metaplasia is produced, product has the electrochemistry gram volume of superelevation
Feature, there is provided a kind of activation strategy of the electrode slice based on passive metal powder, and the potentiality with large-scale application.
Description of the drawings
Fig. 1 is the TEM phenograms of the metallic lithium powder particle of the present invention；
Fig. 2 is the SEM phenograms before the metallic lithium powder/graphite/copper sheet collector electrode slice activation of the present invention；
Fig. 3 is the SEM phenograms after the metallic lithium powder/graphite/copper sheet collector electrode slice activation of the present invention.
Specific embodiment
Below in conjunction with the accompanying drawings technical scheme is illustrated with embodiment.
Embodiment 1, is shown in Fig. 1 to Fig. 3：
The present invention provides a kind of electrode slice activation method based on passive metal lithium powder negative pole, comprise the steps：
1) coating machine is adopted uniformly to be coated to copper the SBR/ toluene solutions that the mass concentration containing metallic lithium powder is 2%
Piece is on the graphite electrode piece of collector, to obtain metallic lithium powder/graphite/copper electrode piece；
2) metallic lithium powder/graphite/copper electrode piece is transferred to the glove box of argon gas protection, 4h is dried at 60 DEG C, it is standby；
3) by dried metallic lithium powder/graphite/copper electrode piece (92 microns of gross thickness) in the glove box that argon gas is protected
Roll-in is carried out using roll squeezer, roll squeezer roll gap is controlled for 60 microns, allows metallic lithium powder/graphite/copper electrode piece at the uniform velocity to pass through roller
Seam carries out roll-in activation；
4) metallic lithium powder/graphite/copper electrode piece after roll-in is activated is stored in standby in the glove box of argon gas protection.
From TEM (transmission electron microscope) phenogram (Fig. 1) of metallic lithium powder particle as can be seen that being given birth to by organic silicone oil
There is one layer of passivation layer due to the generation of side reaction in the metallic lithium powder surface of output, its Main Ingredients and Appearance is lithium carbonate, lithia
Deng.The presence of the passivation layer, can hinder the abjection of lithium metal lithium ion in the electrolytic solution, and increase the internal resistance of cell.Therefore, lead to
Cross rational method metallic lithium powder outer passivation layer is carried out into activation and be highly desirable to.
From scanning electron microscope (SEM) photograph (SEM) piece, it is apparent that comparing the metallic lithium powder/graphite/copper electrode piece before roll-in
(Fig. 2), the metallic lithium powder/graphite after roll-in/copper electrode piece (Fig. 3) is more smooth, and before roll-in electrode slice surface size compared with
Big particle is crushed by mechanical external force.After roll-in, there is lithium metal gloss in the electrode slice surface containing metallic lithium powder.
Above example only to illustrative and not limiting technical scheme, although above-described embodiment enters to the present invention
Detailed description is gone, the person skilled of this area should be understood：The present invention can be modified or be replaced on an equal basis, but
Any modification and local without departing from spirit and scope of the invention is replaced and all should covered in scope of the presently claimed invention.
Claims (4)
1. a kind of electrode slice activation method based on passive metal lithium powder negative pole, it is characterised in that comprise the steps：
1) coating machine is adopted uniformly to be coated to the stone with copper sheet as collector the butadiene-styrene rubber/toluene solution containing metallic lithium powder
On electrode ink piece, metallic lithium powder/graphite/copper electrode piece is obtained；
2) metallic lithium powder/graphite/copper electrode piece is transferred to the glove box of argon gas protection, is dried, it is standby；
3) dried metallic lithium powder/graphite/copper electrode piece is carried out into roll-in in the glove box that argon gas is protected using roll squeezer
Activation；
4) metallic lithium powder/graphite/copper electrode piece after roll-in is activated is stored in standby in the glove box of argon gas protection.
2. the electrode slice activation method based on passive metal lithium powder negative pole according to claim 1, it is characterised in that described
The mass concentration of butadiene-styrene rubber is 2% in butadiene-styrene rubber/toluene solution.
3. the electrode slice activation method based on passive metal lithium powder negative pole according to claim 1, it is characterised in that described
Temperature when being dried in glove box is 60 DEG C, and drying time is 4h.
4. the electrode slice activation method based on passive metal lithium powder negative pole according to claim 1, it is characterised in that described
Roll squeezer roll gap size is controlled when roll-in is activated, allows metallic lithium powder/graphite/copper electrode piece at the uniform velocity to pass through roll squeezer roll gap.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710054465.9A CN106654160A (en) | 2017-01-24 | 2017-01-24 | Electrode plate activation method for negative electrode based on passivation metal lithium powder |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710054465.9A CN106654160A (en) | 2017-01-24 | 2017-01-24 | Electrode plate activation method for negative electrode based on passivation metal lithium powder |
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| CN106654160A true CN106654160A (en) | 2017-05-10 |
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| CN201710054465.9A Pending CN106654160A (en) | 2017-01-24 | 2017-01-24 | Electrode plate activation method for negative electrode based on passivation metal lithium powder |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3660962A4 (en) * | 2017-07-26 | 2021-06-23 | China Energy Cas Technology Co., Ltd. | Lithium metal-skeletal carbon composite material with hydrophobic cladding layer and preparation method and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1290209C (en) * | 2001-12-19 | 2006-12-13 | Fmc公司 | Dispersion of lithium metal in anode of secondarycell |
| CN104993098A (en) * | 2015-06-10 | 2015-10-21 | 中航锂电（洛阳）有限公司 | Lithium supplement negative electrode piece, preparing method thereof, lithium-ion supercapacitor and lithium-ion battery |
| CN105845894A (en) * | 2016-05-04 | 2016-08-10 | 合肥国轩高科动力能源有限公司 | Pre-lithiation method and device for negative pole pieces of lithium-ion battery |
-
2017
- 2017-01-24 CN CN201710054465.9A patent/CN106654160A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1290209C (en) * | 2001-12-19 | 2006-12-13 | Fmc公司 | Dispersion of lithium metal in anode of secondarycell |
| CN104993098A (en) * | 2015-06-10 | 2015-10-21 | 中航锂电（洛阳）有限公司 | Lithium supplement negative electrode piece, preparing method thereof, lithium-ion supercapacitor and lithium-ion battery |
| CN105845894A (en) * | 2016-05-04 | 2016-08-10 | 合肥国轩高科动力能源有限公司 | Pre-lithiation method and device for negative pole pieces of lithium-ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3660962A4 (en) * | 2017-07-26 | 2021-06-23 | China Energy Cas Technology Co., Ltd. | Lithium metal-skeletal carbon composite material with hydrophobic cladding layer and preparation method and use thereof |
| US11462741B2 (en) | 2017-07-26 | 2022-10-04 | China Energy Cas Technology Co., Ltd. | Metallic lithium-skeleton carbon composite material having a hydrophobic cladding layer, preparation method and use thereof |
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Application publication date: 20170510 |