CN108470879A - A kind of large-scale method for producing of lithium copper composite metal negative plate - Google Patents
A kind of large-scale method for producing of lithium copper composite metal negative plate Download PDFInfo
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- CN108470879A CN108470879A CN201810358135.3A CN201810358135A CN108470879A CN 108470879 A CN108470879 A CN 108470879A CN 201810358135 A CN201810358135 A CN 201810358135A CN 108470879 A CN108470879 A CN 108470879A
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- copper
- lithium
- negative plate
- composite metal
- particle
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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
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of large-scale method for producing of lithium copper composite metal negative plate, include the following steps：According to mass ratio（0.5~2）:1 takes passivation of lithium powder and copper particle, and copper particle, solvent, binder and passivation of lithium powder are uniformly mixed and obtain slurry；Slurry is coated on substrate, dry 0.5 under the conditions of vacuum and 25~60 DEG C~for 24 hours, it is evaporated completely solvent, obtains lithium copper composite metal negative plate.The negative plate for the three-dimensional porous structure that the method for the present invention obtains, the interior contact resistance of copper and lithium is not only reduced, and the formation of dendrite lithium can be effectively inhibited, prevents the safety issues such as battery short circuit caused by cyclic process, greatly improve the safety of battery, stability and service life.
Description
Technical field
The present invention relates to a kind of preparation method of lithium metal battery negative plate, especially a kind of lithium copper composite metal negative plate
Large-scale method for producing, belong to energy-storage battery technical field.
Background technology
Lithium an- ode is with 3860mAhg-1High power capacity and become relative to -3.040V the potentials of standard hydrogen electrode
The ideal negative material of energy storage field innovation, therefore receive the extensive concern of scientific research personnel and enterprisers.In addition, using lithium
Metal negative electrode is served as to be able to obtain 2600Whkg to electrode to assemble lithium-sulfur cell and lithium-air battery-1With 3500
Wh·kg-1High-energy density.Lithium metal has great advantage, however the peace encountered in actual application in the battery
Full sex chromosome mosaicism, such as the Li/TiS commercially produced in 19792Battery one comes out the problem of there have been battery explosions, this be because
For when lithium is as battery cathode, the surface of lithium metal is when this smooth lithium piece surface deposits in cyclic process, due to point
Sedimentary effect is held, the lithium of subsequent deposition can be grown along the lithium first deposited, and then form Li dendrite, and the continued propagation of dendrite lithium is just
Diaphragm can be pierced through and cause battery short circuit and the explosion that causes battery.Therefore, novel lithium metal negative material being capable of dendrite inhibition lithium
Be grown to serve as high energy density cells（Such as lithium-sulfur cell and lithium-air battery etc.）The key of commercial application.
Invention content
It is an object of the invention to：In view of the defects existing in the prior art, a kind of lithium copper composite metal negative plate is proposed
Large-scale method for producing will be passivated after lithium powder is mixed with copper particle powder using simple method and be obtained coated in copper foil surface
Lithium copper composite metal negative plate not only reduces the interior contact resistance of copper and lithium, is pressed down by the three-dimensional structure of copper particle sub-electrode
Dendrite lithium during circulating battery processed generates, and reduces the security risk of battery, increases battery life and stability, and
Easy to operate, pollution is small, and low energy consumption, at low cost.
In order to reach object above, the present invention provides a kind of large-scale method for producing of lithium copper composite metal negative plate,
Include the following steps：
The first step, according to mass ratio（0.5~2）:1 takes passivation of lithium powder and copper particle, by copper particle, solvent, binder and passivation
Lithium powder is uniformly mixed and obtains slurry；
Second step coats slurry on substrate, dry 0.5 under the conditions of vacuum and 25~60 DEG C~for 24 hours, and it is evaporated completely solvent,
Obtain lithium copper composite metal negative plate.
The present invention is regulated and controled mass ratio to optimum range so that copper by the mass ratio of regulation and control passivation of lithium powder and copper particle
The three-dimensional structure that particle is constructed can accommodate lithium well, and the quality for regulating and controlling lithium disclosure satisfy that needed for battery without generating lithium
Waste.
The present invention constructs three-dimensional conductive frame using copper particle, is due to serving as cathode using lithium piece or lithium powder first
Material can not accomplish that Li dendrite formation and growth, the present invention is inhibited to be not only as a kind of conductive frame using copper particle
Play conductive effect, in specific battery structure, copper particle also with passivation of lithium powder（Lithium particle）One be mixed to get
The uniform bulk structure of kind, in the practical work process of battery, such as de- lithium process, lithium are deviate from from cathode, leave behind three-dimensional
Copper particle subframe, copper particle subframe at this time remain on very high electric conductivity in order to the deposition next time of lithium；Then, this
Copper particle provides abundant channel for the deposition of later stage lithium and abjection, finally, can be realized pair by the mass ratio both regulated and controled
The control of lithium amount, within the scope of above-mentioned mass ratio, copper provides support carrier for the deposition of lithium and abjection, and can be at this
Work of a quality than ensureing battery stability and high efficiency in range.
Preferably, the copper particle is technical grade copper nano-particle or copper micro particles.The present invention by introduce copper particle,
The deposition for being later stage lithium between copper particle provides larger deposition space, and more by the three-dimensional that this copper particle is built
Hole conductive frame supports volume expansion of the lithium in cyclic process, it can be achieved that the lithium of more capacity deposits.
Preferably, the copper particle is mixed with copper micro particles by copper nano-particle and is formed, the copper micro particles and copper
The mass ratio of nano-particle is（1~9）：（1~9）.
It is further preferred that a diameter of 100~500nm of the copper nano-particle；A diameter of the 1 of the copper micro particles
~5 μm.
Preferably, the coating method is blade coating, spraying, spin coating or silk-screen printing.Wherein, spraying method is using industrial
Spray gun is sprayed, and spin coating mode carries out spin coating using spin coating instrument, and blade coating mode is scratched using business with scraper, screen printing
Brush mode carries out silk-screen printing using screen process press.
Preferably, in the first step, after being scattered in solvent after copper particle and passivation of lithium powder mixing, then binder is added simultaneously
It stirs evenly, obtains slurry.
It is further preferred that the solvent is toluene or N, N dimethyl pyrrolidones（NMP）；The binder is poly- inclined
Vinyl fluoride（PVDF）, polytetrafluoroethylene (PTFE)（PTFE）Or emulsion acrylic resin（PAA）.
Preferably, the copper particle using ultra-pure water, acetone, ethyl alcohol before use, be respectively washed three times, then in vacuum
It is dried under environment.
Preferably, the substrate is that business polishes copper foil, and thickness is 10~300 μm.
It is an advantage of the invention that：The negative plate for the three-dimensional porous structure that the method for the present invention obtains, not only reduces copper and lithium
Interior contact resistance, and the formation of dendrite lithium can be effectively inhibited, prevent battery short-circuit caused by cyclic process
Etc. safety issues, greatly improve the safety of battery, stability and service life.
Description of the drawings
The present invention will be further described below with reference to the drawings.
Fig. 1 is the flow chart of the present invention.
Specific implementation mode
Embodiment 1
1 kilogram of business is taken to use ultra-pure water, ethyl alcohol, acetone to be respectively washed three times to remove copper micron grain with copper micro particles powder
The impurity such as the grease in sublist face, by the copper micro particles obtained after cleaning the vacuum drying 6h copper micro particles powder that obtains that treated
End.
It takes 1 kilogram of business passivation of lithium powder that the glass being placed in argon gas gloves for protection case is added with copper micro particles powder to hold
1h is stirred in device to being uniformly mixed, whole whipping temp is 25 degrees Celsius.100 grams of PVDF are added into glass container again as viscous
It ties agent and 0.5 kilogram of NMP and is used as solvent, be uniformly mixing to obtain copper lithium slurry and stay and do spare, whole whipping temp is Celsius for 25
Degree.
The scraper that specification is 100 microns is chosen by the slurry even application mixed on copper foil, the surface area of copper foil is 1
Square metre, obtain coated pole piece.Coated pole piece is dry under argon atmosphere protection（60 degrees Celsius）It is multiple to obtain copper lithium
Close pole piece.Then, copper lithium composite pole piece punching is molded according to the size of battery pole piece.
Selection battery model is 2032 type button cells, therefore pole piece diameter is set to 12 millimeters, obtained pole
Piece is copper lithium composite negative pole.Copper lithium composite negative pole battery pack is tested into voltage delay feelings under its high current in Symmetrical cells
Condition, test value 10mV, it was demonstrated that this copper lithium composite negative pole stability is fine.
Embodiment 2
1 kilogram of business is taken to use ultra-pure water, ethyl alcohol, acetone to be respectively washed three times to remove copper micron grain with copper micro particles powder
The impurity such as the grease in sublist face, by the copper micro particles obtained after cleaning the vacuum drying 6h copper micro particles powder that obtains that treated
End.
2 kilograms of business passivation of lithium powder is taken to be added to the glass being placed in argon gas gloves for protection case with copper micro particles powder
1h is stirred in container to being uniformly mixed, whole whipping temp is 25 degrees Celsius.100 grams of PVDF are added in glass container as viscous
It ties agent and 0.5 kilogram of NMP and is used as solvent, be uniformly mixing to obtain copper lithium slurry and stay and do spare, whole whipping temp is Celsius for 25
Degree.
The scraper that specification is 100 microns is chosen by the slurry even application mixed on copper foil, the surface area of copper foil is 1
Square metre, obtain coated pole piece.Coated pole piece is dry under argon atmosphere protection（60 degrees Celsius）Obtain copper lithium
Composite pole piece.Copper lithium composite pole piece punching is molded according to the size of battery pole piece.
Selection battery model is 2032 type button cells, therefore pole piece diameter is set to 12 millimeters, obtained pole
Piece is copper lithium composite negative pole.Copper lithium composite negative pole battery pack is tested into voltage delay feelings under its high current in Symmetrical cells
Condition, test value 50mV, it was demonstrated that this copper lithium composite negative pole stability is preferable.
Embodiment 3
1 kilogram of business is taken to use ultra-pure water, ethyl alcohol, acetone to be respectively washed three times to remove copper nanoparticle with copper nano-particle powder
The impurity such as the grease in sublist face, by the copper nano-particle obtained after cleaning the vacuum drying 6h copper nano-particle powder that obtains that treated
End.
2 kilograms of business passivation of lithium powder is taken to be added to the glass being placed in argon gas gloves for protection case with copper nano-particle powder
1h is stirred in container to being uniformly mixed, whole whipping temp is 25 degrees Celsius.100 grams of PTFE conducts are added in glass container
Binder and 0.5 kilogram of toluene uniformly obtain copper lithium slurry as stirring solvent and stay to do spare, and whole whipping temp is 25 Celsius
Degree.
The scraper that specification is 100 microns is chosen by the slurry even application mixed on copper foil, the surface area of copper foil is 1
Square metre, obtain coated pole piece.Coated pole piece is dry under argon atmosphere protection（60 degrees Celsius）Obtain copper lithium
Composite pole piece.Copper lithium composite pole piece punching is molded according to the size of battery pole piece.
The battery model of selection is 2032 type button cells, therefore pole piece diameter is set to 12 millimeters, obtains
Pole piece is copper lithium composite negative pole.Copper lithium composite negative pole battery pack is tested into voltage delay feelings under its high current in Symmetrical cells
Condition, test value 15mV, it was demonstrated that this copper lithium composite negative pole stability is fine.
In addition to the implementation, the present invention can also have other embodiment.It is all to use equivalent substitution or equivalent transformation shape
At technical solution, fall within the scope of protection required by the present invention.
Claims (9)
1. a kind of large-scale method for producing of lithium copper composite metal negative plate, which is characterized in that include the following steps：
The first step, according to mass ratio（0.5~2）:1 takes passivation of lithium powder and copper particle, by copper particle, solvent, binder and passivation
Lithium powder is uniformly mixed and obtains slurry；
Second step coats slurry on substrate, dry 0.5 under the conditions of vacuum and 25~60 DEG C~for 24 hours, and it is evaporated completely solvent,
Obtain lithium copper composite metal negative plate.
2. a kind of large-scale method for producing of lithium copper composite metal negative plate according to claim 1, which is characterized in that described
Copper particle is copper nano-particle or copper micro particles.
3. a kind of large-scale method for producing of lithium copper composite metal negative plate according to claim 1, which is characterized in that described
Copper particle is mixed with copper micro particles by copper nano-particle and is formed, and the mass ratio of the copper micro particles and copper nano-particle is（1
~9）：（1~9）.
4. according to a kind of large-scale method for producing of lithium copper composite metal negative plate described in Claims 2 or 3, which is characterized in that
A diameter of 100~500nm of the copper nano-particle；A diameter of 1~5 μm of the copper micro particles.
5. a kind of large-scale method for producing of lithium copper composite metal negative plate according to claim 1, which is characterized in that described
Coating method is blade coating, spraying, spin coating or silk-screen printing.
6. a kind of large-scale method for producing of lithium copper composite metal negative plate according to claim 1, which is characterized in that first
In step, after copper particle is scattered in solvent, adds binder and stir evenly, add passivation of lithium powder, be uniformly mixing to obtain
Slurry.
7. a kind of large-scale method for producing of lithium copper composite metal negative plate according to claim 6, which is characterized in that described
Solvent is toluene or N, N dimethyl pyrrolidones；The binder is Kynoar, polytetrafluoroethylene (PTFE) or acrylic resin breast
Liquid.
8. a kind of large-scale method for producing of lithium copper composite metal negative plate according to claim 1, which is characterized in that described
Then copper particle is dried before use, be respectively washed three times using ultra-pure water, acetone, ethyl alcohol under vacuum environment.
9. a kind of large-scale method for producing of lithium copper composite metal negative plate according to claim 1, which is characterized in that described
Substrate is that business polishes copper foil, and thickness is 10~300 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810358135.3A CN108470879A (en) | 2018-04-20 | 2018-04-20 | A kind of large-scale method for producing of lithium copper composite metal negative plate |
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| CN201810358135.3A CN108470879A (en) | 2018-04-20 | 2018-04-20 | A kind of large-scale method for producing of lithium copper composite metal negative plate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109659495A (en) * | 2018-11-20 | 2019-04-19 | 湖南立方新能源科技有限责任公司 | A kind of lithium metal battery positive plate and lithium metal battery |
| CN109837561A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of metallic lithium powder and its electrochemical preparation method |
| CN112271287A (en) * | 2020-09-27 | 2021-01-26 | 天津师范大学 | Gridding lithium metal negative electrode and preparation method and application thereof |
| CN114628686A (en) * | 2022-03-11 | 2022-06-14 | 南京邮电大学 | Production method of porous copper micron hollow sphere current collector |
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| CN105932295A (en) * | 2016-04-22 | 2016-09-07 | 清华大学深圳研究生院 | Metal lithium secondary battery and negative electrode and porous copper current collector thereof |
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2018
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| CN105552307A (en) * | 2016-02-03 | 2016-05-04 | 宁波良能新材料有限公司 | Negative electrode material of lithium-sulfur battery and preparation method of negative electrode material |
| CN105932295A (en) * | 2016-04-22 | 2016-09-07 | 清华大学深圳研究生院 | Metal lithium secondary battery and negative electrode and porous copper current collector thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109837561A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of metallic lithium powder and its electrochemical preparation method |
| CN109659495A (en) * | 2018-11-20 | 2019-04-19 | 湖南立方新能源科技有限责任公司 | A kind of lithium metal battery positive plate and lithium metal battery |
| CN112271287A (en) * | 2020-09-27 | 2021-01-26 | 天津师范大学 | Gridding lithium metal negative electrode and preparation method and application thereof |
| CN114628686A (en) * | 2022-03-11 | 2022-06-14 | 南京邮电大学 | Production method of porous copper micron hollow sphere current collector |
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