CN110233242A - A kind of lithium composite negative pole sheet material and preparation method thereof - Google Patents
A kind of lithium composite negative pole sheet material and preparation method thereof Download PDFInfo
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- CN110233242A CN110233242A CN201810182572.4A CN201810182572A CN110233242A CN 110233242 A CN110233242 A CN 110233242A CN 201810182572 A CN201810182572 A CN 201810182572A CN 110233242 A CN110233242 A CN 110233242A
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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
- 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
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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
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
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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
- H01M4/134—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
- H01M4/13—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
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of lithium composite negative pole sheet materials and preparation method thereof.The lithium composite negative pole sheet material includes metal pour lithium slice, binder (mixing of one or both of CMC, SBS, PVDF, PTFE or more) and carbon material (mixing of one of graphite, acetylene black, carbon nanotube and graphene or two kinds or more).The lithium composite negative pole sheet material can be applied in lithium ion battery, can also apply in the batteries such as thermal cell, lithium-sulfur cell, lithium manganese dioxide cell.
Description
Technical field
The present invention relates to lithium electrode field of material preparation, and in particular to a kind of lithium composite negative pole sheet material and its preparation side
Method.
Background technique
Lithium metal has high theoretical specific capacity (3860 mAh/g) and ideal cathode potential (- 3.04 V vs.
SHE), the most promising negative electrode material of lithium metal secondary battery is become.Using lithium metal as the secondary cell of cathode, there is height
The advantages such as operating voltage, high-energy density, so that lithium metal becomes the preferred material in current energy storage field.However, existing
It is growing not to be able to satisfy consumer for lithium ion secondary battery indices capacity, cycle life, charge/discharge speed etc.
Demand, this is because lithium metal secondary battery there is a problem of in application two it is extremely important: first, Li dendrite problem.
It because lithium metal is more active, can be chemically reacted with electrolyte when lithium metal is as cathode, form Li dendrite knot
Structure, such result are exactly that the growth of battery Li dendrite during charge and discharge cycles will pierce through diaphragm and cause inside battery
Short-circuit and serious safety problem, and the repetition for also resulting in SEI film destroys and causes anti-between lithium metal and electrolyte
It answers.Second, lithium metal secondary battery cycle efficieny is lower.And cause cycle efficieny low there are two main cause: charge and discharge cycles
The repetition of the SEI film of metallic lithium surface is destroyed and is repaired in the process, and then is consumed lithium metal and shortened battery life;It is irreversible
The generation of " dead lithium " (dendrite lithium separated from main body lithium) can also reduce the capacity of lithium metal battery.
Therefore, how preferable theoretical specific capacity and lower cathode possessed by lithium metal are preferably utilized in lithium battery
The powerful advantage of current potential, and avoid above-mentioned lithium metal as the electrode material institute problem, a kind of novel composite negative pole containing lithium
The research and development of material become the most important thing of the invention.
Summary of the invention
The present invention provides a kind of lithium composite negative pole sheet material and its system for defect involved in above-mentioned background technique
Preparation Method.The present invention by common electrode carbon material (one of graphite, acetylene black, carbon nanotube and graphene or two kinds and with
On mixing) with metal lithium sheet carbon film/lithium metal membrane lithium composite negative pole sheet material layer by layer prepared by the technique of double roller roll-in, it is sharp
The advantages such as high conductivity and the performance stabilization with these carbon materials, while keeping lithium height ratio capacity and low negative potential, effectively
Solve the problems, such as lithium dendrite growth, and then internal short-circuit of battery, SEI film repeat to destroy caused by avoiding because of lithium dendrite growth
The problems such as low with cycle efficieny.Also, the preparation method is relatively simple, is easy to industrialization.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of lithium composite negative pole sheet material, including metal pour lithium slice, binder (one of CMC, SBS, PVDF, PTFE or two
Kind or more mixing) and carbon material (one of graphite, acetylene black, carbon nanotube and graphene or two kinds or more it is mixed
It closes).
Further, in the lithium composite negative pole sheet material, binder include one of CMC, SBS, PVDF, PTFE or
Two kinds or more of mixing, wherein the content of binder is 0.1-6.0% in lithium combination electrode material.
Further, the binder is usually the powder of CMC, SBS, PVDF, PTFE etc., and the binder makes
With preceding, first to dissolve and be dispersed in NMP stand-by, storage time must not exceed 10h.
In the lithium composite negative pole sheet material, the carbon material includes in graphite, acetylene black, carbon nanotube and graphene
One or two kinds of or more mixing, wherein the content of carbon material is 1-75% in lithium composite negative pole sheet material.
Further, the lithium composite negative pole sheet material, specific preparation method is:
1) first the dissolution of binder powder is dispersed in nmp solvent stand-by;
2) toluene solvant is added into load weighted carbon material, be then added dropwise thereto it is above-mentioned 1) in binder solution, pass through
Abundant ultrasound simultaneously stirs (or using Vacuum mixer), is allowed to uniformly mixed, obtains carbon material slurry.
3) by it is above-mentioned 2) in carbon material slurry be transferred in the multifunctional hand casing full of argon gas, rolled several times through double roller
Sheet is made, is then overlaped again with pure lithium metal piece, by multiple " roll-in-folding-roll-in again " in double roller
Film-making is mixed, lithium composite negative pole sheet material head product is obtained.
4) by it is above-mentioned 3) in lithium composite negative pole sheet material head product obtained put vacuum oven into, carried out under certain temperature
Vacuum drying, it is final to obtain lithium composite negative pole sheet material.
Further, described 1) first to dissolve binder powder in the lithium composite negative plate material preparation method
It is dispersed in nmp solvent, wherein the mass ratio of NMP and binder powder are as follows: 10:1-20:1.
In the lithium composite negative plate material preparation method, it is described 2) in toluene solvant and the mass ratio of carbon material be
1:1-10:1。
In the lithium composite negative plate material preparation method, it is described 3) in the multifunctional hand casing full of argon gas,
Wherein control oxygen content is less than 1ppm, and moisture content is less than 0.1PPm.
In the lithium composite negative plate material preparation method, it is described 3) in twin-roll machine be superhigh precision roll squeezer, can
To control the roller spacing between rolling temperatures and double roller well.Wherein, the use temperature range of twin-roll machine is: 40-120 DEG C
In the lithium composite negative plate material preparation method, it is described 4) in vacuum drying temperature range be 60-120 DEG C, do
The dry time is generally 8-48 hours, and the pressure of vacuum oven is 0.1Mpa.
Further, the thickness of the lithium composite negative pole sheet material, the electrode slice can be by adjusting double roller roller spacing
Size control, it is final dry after the gained composite negative pole material lamellar spacing be 5um-2mm.
The lithium composite negative pole sheet material, can apply in lithium ion battery, can also apply in thermal cell, lithium sulphur
In the batteries such as battery, lithium manganese dioxide cell.
The beneficial effects of the present invention are:
The present invention provides a kind of lithium composite negative pole sheet materials and preparation method thereof, by common electrode carbon material (graphite, acetylene
The mixing of one of black, carbon nanotube and graphene or two kinds or more) the technique system that passes through double roller roll-in with metal lithium sheet
Standby carbon film/lithium metal membrane lithium composite negative pole sheet material layer by layer the advantages such as stablizes using the high conductivity and performance of these carbon materials,
While keeping lithium height ratio capacity and low negative potential, effectively lithium dendrite growth is solved the problems, such as, and then avoid because Li dendrite is raw
Internal short-circuit of battery, SEI film repeat to destroy the problems such as low with cycle efficieny caused by length.Also, carbon material also has more
Stable configuration state may act as skeleton function in lithium composite negative pole material.Meanwhile the preparation method technique is relatively simple,
Cost is more cheap, is highly susceptible to industrialization.
Specific embodiment
The present invention is specifically described below with reference to embodiment, but embodiments of the present invention are not limited only to this, herein
On the basis of slightly change and this material application range, all fall within the protection scope of the present invention.
Embodiment 1
1) first the dissolution of 1.67g binder PTFE powder is dispersed in 5gNMP solvent stand-by;
2) graphite and each 5g of carbon nanotube are weighed in beaker, 20ml toluene is added, then the NMP of PTFE is added dropwise in stirring premix
Solution by sufficiently ultrasound and stirs (or using Vacuum mixer), is allowed to uniformly mixed, obtains carbon material slurry.
3) double roller is opened, adjusts temperature to 60 DEG C of preheating 20min.By it is above-mentioned 2) in carbon material slurry be transferred to full of argon gas
Multifunctional hand casing in, rolled through double roller several all over making sheet, then overlap one with the pure lithium metal piece of 88.33g again
It rises, mixes film-making by multiple " roll-in-folding-roll-in again " in double roller, lithium composite negative pole sheet material head product is made.
4) by it is above-mentioned 3) in lithium composite negative pole sheet material head product obtained put vacuum oven into, 80 DEG C of progress vacuum are dry
Dry 24 hours, final to obtain lithium composite negative pole sheet material, which is 20um.
Embodiment 2
1) first the dissolution of 10g binder PVDF powder is dispersed in 15gNMP solvent stand-by;
2) graphite and each 50g of carbon nanotube are weighed in Vacuum mixer, 200ml toluene is added, then stirring premix is added dropwise
The nmp solution of PVDF, is sufficiently stirred, and is allowed to uniformly mixed, obtains carbon material slurry.
3) double roller is opened, adjusts temperature to 80 DEG C of preheating 20min.By it is above-mentioned 2) in carbon material slurry be transferred to full of argon gas
Multifunctional hand casing in, roll through double roller several all over making sheet, then overlap again with the pure lithium metal piece of 890g,
Film-making is mixed by multiple " roll-in-folding-roll-in again " in double roller, lithium composite negative pole sheet material head product is made.
4) by it is above-mentioned 3) in the lithium composite negative pole sheet material head product that is worth put vacuum oven into, 60 DEG C of progresss vacuum are done
Dry 48 hours, final to obtain lithium composite negative pole sheet material, which is 15um.
Claims (10)
1. a kind of lithium composite negative pole sheet material, including metal pour lithium slice, binder (one of CMC, SBS, PVDF, PTFE or
Two kinds or more of mixing) and carbon material (one of graphite, acetylene black, carbon nanotube and graphene or two kinds or more
Mixing).
2. lithium composite negative pole sheet material as described in claim 1, the binder includes one in CMC, SBS, PVDF, PTFE
Kind or two kinds or more of mixing, wherein in lithium combination electrode material, the content of binder is 0.1-6.0%, and the bonding
Agent is dispersed in NMP for use before use, first to dissolve, and storage time must not exceed 10h.
3. lithium composite negative pole sheet material as described in claim 1, the carbon material include graphite, acetylene black, carbon nanotube and
The mixing of one or both of graphene or more, wherein the content of carbon material is 1-75% in lithium composite negative pole material.
4. lithium composite negative pole sheet material as described in claim 1, specific preparation method is:
The dissolution of binder powder is first dispersed in nmp solvent stand-by by a;
Toluene solvant is added into load weighted carbon material by b, be then added dropwise thereto it is above-mentioned a) in binder solution, through overcharging
Divide ultrasound and stir (or using Vacuum mixer), is allowed to uniformly mixed, obtains carbon material slurry;
Carbon material slurry is transferred in the multifunctional hand casing full of argon gas by c, is rolled several times through double roller and is made sheet, so
It overlaps again with pure lithium metal piece afterwards, mixes film-making by multiple " roll-in-folding-roll-in again " in double roller, obtain
Lithium composite negative pole sheet material head product;
D puts lithium composite negative pole sheet material head product into vacuum oven, is dried in vacuo under certain temperature, finally obtains lithium
Composite negative pole sheet material.
5. described a) first by the dissolution point of binder powder in lithium composite negative plate material preparation method as claimed in claim 4
Be dispersed in nmp solvent, wherein the mass ratio of NMP and binder powder are as follows: 1:1-20:1, it is described b) in toluene solvant and carbon materials
The mass ratio of material is 1:1-10:1.
6. in lithium composite negative plate material preparation method as claimed in claim 4, it is described c) in it is multi-functional full of argon gas
Glove box, wherein control oxygen content is less than 1ppm, moisture content is less than 0.1ppm.
7. in lithium composite negative plate material preparation method as claimed in claim 4, it is described c) in twin-roll machine be superhigh precision
Roll squeezer can be very good the roller spacing between control rolling temperatures and double roller, wherein the use temperature range of twin-roll machine is: 40-
120℃。
8. in lithium composite negative plate material preparation method as claimed in claim 4, it is described d) in vacuum drying temperature range
It is 60-120 DEG C, drying time is generally 8-48 hours, and the pressure of vacuum oven is 0.1Mpa.
9. the thickness of the lithium composite negative pole sheet material as described in claim 1 and 4, the electrode slice can be by between adjusting double roller roller
Away from size control, the gained composite negative pole material lamellar spacing is 5um-2mm after final drying.
10. the lithium composite negative pole sheet material as described in claim 1 and 4, can apply in lithium ion battery, can also apply
In the batteries such as thermal cell, lithium-sulfur cell, lithium manganese dioxide cell.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112072099A (en) * | 2020-08-10 | 2020-12-11 | 贵州众智华创电子科技有限公司 | Positive electrode material of lithium battery and manufacturing method thereof |
TWI736211B (en) * | 2020-04-08 | 2021-08-11 | 大陸商烯美科技(深圳)有限公司 | Graphene thermal battery structure |
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Publication number | Priority date | Publication date | Assignee | Title |
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US4615959A (en) * | 1984-05-07 | 1986-10-07 | Sanyo Chemical Industries, Ltd. | Secondary battery or cell with improved rechargeability |
JPH11135116A (en) * | 1997-10-27 | 1999-05-21 | Fuji Elelctrochem Co Ltd | Negative electrode for lithium secondary battery, lithium secondary battery using the negative electrode, and manufacture of the negative electrode for the lithium secondary battery |
KR20010037101A (en) * | 1999-10-13 | 2001-05-07 | 김덕중 | Lithium secondary battery cathode composition, lithium secondary battery cathode and lithium secondary battery employing the same, and method for preparing the same |
CN1889288A (en) * | 2006-07-14 | 2007-01-03 | 清华大学 | Method for producing hard carbon lithium metal composite negative pole material for lithium ion battery |
-
2018
- 2018-03-06 CN CN201810182572.4A patent/CN110233242A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4615959A (en) * | 1984-05-07 | 1986-10-07 | Sanyo Chemical Industries, Ltd. | Secondary battery or cell with improved rechargeability |
JPH11135116A (en) * | 1997-10-27 | 1999-05-21 | Fuji Elelctrochem Co Ltd | Negative electrode for lithium secondary battery, lithium secondary battery using the negative electrode, and manufacture of the negative electrode for the lithium secondary battery |
KR20010037101A (en) * | 1999-10-13 | 2001-05-07 | 김덕중 | Lithium secondary battery cathode composition, lithium secondary battery cathode and lithium secondary battery employing the same, and method for preparing the same |
CN1889288A (en) * | 2006-07-14 | 2007-01-03 | 清华大学 | Method for producing hard carbon lithium metal composite negative pole material for lithium ion battery |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI736211B (en) * | 2020-04-08 | 2021-08-11 | 大陸商烯美科技(深圳)有限公司 | Graphene thermal battery structure |
CN112072099A (en) * | 2020-08-10 | 2020-12-11 | 贵州众智华创电子科技有限公司 | Positive electrode material of lithium battery and manufacturing method thereof |
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Application publication date: 20190913 |