CN109309194A - It is modified without cathode of lithium, preparation method and contains its lithium ion battery - Google Patents
It is modified without cathode of lithium, preparation method and contains its lithium ion battery Download PDFInfo
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- CN109309194A CN109309194A CN201710618085.3A CN201710618085A CN109309194A CN 109309194 A CN109309194 A CN 109309194A CN 201710618085 A CN201710618085 A CN 201710618085A CN 109309194 A CN109309194 A CN 109309194A
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/13—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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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
Abstract
A kind of modification is disclosed without cathode of lithium, preparation method and containing its lithium ion battery.It is modified without cathode of lithium other than no lithium titanate cathode material, also contains lithium metal-skeleton carbon composite, the lithium metal-skeleton carbon composite content is the 2%-20% of negative electrode active material quality by percentage to the quality.In the charge and discharge process of battery for the first time, the lithium metal in lithium metal-framework carbon material can replenish no cathode of lithium surface form SEI layer consumed by lithium, thus first charge-discharge efficiency of the raising without cathode of lithium.
Description
Technical field
The present invention relates to a kind of technical field of nano material, in particular to a kind of modification without cathode of lithium, preparation method and
Contain its lithium ion battery.
Background technique
Lithium battery has the features such as high-energy density, good cyclical stability, safety, sets in portable electronic piece
It is standby, it is widely used in electric car and power grid energy storage.Graphite is the reticular structure stacked in multi-layers of six-membered carbon ring composition
The layer structure of formation, the layer structure are conducive to lithium ion lithium ion in the deintercalation of its interlayer, charging and are embedded into interlayer, shape
At compound L iC6, theoretical specific capacity 372mAh/g.In addition to this, deintercalation reaction of the lithium in graphite is on the left side 0-0.25V
The right side has good charge and discharge platform, can be with the positive electrode of offer lithium source, such as cobalt acid lithium, LiMn2O4, lithium nickelate phase
Match, the battery average output voltage of composition is high, it is current commercial Li-ion batteries using most negative electrode materials.
However, since surface will form one layer of solid electrolyte interface film (SEI to graphite electrode during embedding lithium for the first time
Film), the lithium of this layer of SEI film needs is formed from positive electrode, and the reaction for forming SEI film is irreversible reaction, therefore is filled
It can not be emptied back among anode in electric discharge when electric from the lithium ion that anode obtains, cause the loss of cell active materials
And only 80% efficiency for the first time.To play battery capacity completely, the positive electrode of full battery usually requires excess, however by
Higher in positive electrode price, the excessive method of positive electrode is not the perfect way solved the problems, such as.
Japan Patent JP9-330703 has reported a kind of preparation method of graphite-carbon composite graphite negative electrode, and this method will
Organic matter is dissolved in organic reagent, then evaporates dry out solvent after mixing with microlite ink powder, and it is micro- to obtain Coated with Organic Matter graphite
Brilliant material, then the material, so that the clad on surface is carbonized, is obtained into graphite-under an inert atmosphere with 700 DEG C of -900 DEG C of sintering
Carbon composite.Although this kind of material increases as the cycle efficieny for the first time of cathode, material initial stage electric discharge specific volume
Amount only has 240mAh/g, and furthermore the preparation method is complex, and production cost is higher, is unfavorable for extensive industrialization.In in addition,
State's patent 200710072974.0, which is reported, is prepared for a kind of surface modification by the technique that graphite covered by asphalt powder is carbonized again
Graphite so that the cycle efficieny for the first time of the material increases.However, the modified graphite of method preparation is needed in inert gas
Protection under, be sintered with 800 DEG C -1000 DEG C of high temperature, therefore to the more demanding of production equipment, energy consumption is larger.In addition,
This kind is limited to first efficiency raising of the graphite modified method for graphite cathode, and only up to 93.53%.Therefore it is followed for the first time
There are also huge rooms for promotion in terms of the promotion of ring efficiency.
Summary of the invention
One of main object of the present invention be to provide a kind of modification without cathode of lithium, preparation method and containing its lithium from
Sub- battery can be used for improving for the first time cycle efficieny of the lithium ion battery without cathode of lithium.
Present invention employs following technical solutions:
A kind of modification of lithium ion battery is provided in some embodiments without cathode of lithium, wherein the modification is removed without cathode of lithium
Outside without lithium titanate cathode material, also contain lithium metal-skeleton carbon composite, the lithium metal-skeleton carbon composite content
It is by percentage to the quality the 2%-20% of no cathode of lithium active material.
A kind of method of the modification preparing lithium ion battery without cathode of lithium, the method packet are provided in some embodiments
It includes: will be containing whether there is or not the negative electrode material slurries of lithium titanate cathode material and lithium metal-skeleton carbon composite mixture to be coated on metal
On collector, cathode pole piece is formed；Or lithium metal-skeleton carbon composite is dispersed on coated no cathode of lithium pole piece
And no cathode of lithium pole piece is compound in a manner of pressure bonding.
A kind of lithium ion battery is provided in some embodiments, and the lithium ion battery includes that above-mentioned modification is negative without lithium
Pole.
A kind of method improving for the first time cycle efficieny of the lithium ion battery without cathode of lithium is provided in some embodiments, it is described
Method, which is included in no lithium titanate cathode material, combines lithium metal-skeleton carbon composite, the lithium metal-skeleton carbon composite
Content is the 2%-20% of negative electrode material gross mass by percentage to the quality.
The present invention can have at least one of following beneficial effect:
(1) by mixing lithium metal-skeleton carbon composite in no lithium titanate cathode material, in the charge and discharge of battery for the first time
Lithium metal in journey in lithium metal-framework carbon material can replenish no cathode of lithium surface form SEI layers consumed by lithium, thus
The first charge-discharge efficiency without cathode of lithium is improved, is close to 100%.
(2) the modified cyclical stability that battery can be improved without cathode of lithium.
(3) modification of the invention is easy without cathode of lithium preparation process, and low energy consumption, greatly reduces production cost.
(4) present invention requires production establishing low, is suitble to industrialized production.
Detailed description of the invention
Fig. 1 is electric discharge-charge graph for the first time of graphite cathode in embodiment 1.
Fig. 2 is the graphite cathode electric discharge for the first time-charging song for mending lithium in embodiment 1 using lithium metal-skeleton carbon composite
Line chart.
Fig. 3 is graphite cathode and the charge and discharge using lithium metal-skeleton carbon composite benefit lithium graphite cathode in embodiment 1
Electric cyclic curve figure.
Fig. 4 is silicium cathode and putting for the first time using lithium metal-skeleton carbon composite benefit lithium silicium cathode in embodiment 2
Electricity-charge graph.
Fig. 5 is the benefit lithium graphite cathode that obtains electric discharge-charge graph for the first time in embodiment 3.
Fig. 6 is that the capacity of the battery obtained in embodiment 3 keeps curve.
Specific embodiment
One aspect of the present invention provides a kind of modification of lithium ion battery without cathode of lithium, cathode of the modification without cathode of lithium
In material other than no lithium titanate cathode material, also contain lithium metal-skeleton carbon composite.
In some embodiments, the lithium metal-skeleton carbon composite content for no cathode of lithium active material quality
Percentage 2%-20%, for example, 3%-20% perhaps 5%-20% or 5%-15%.
In some embodiments, the lithium metal-skeleton carbon composite includes porous carbon materials carrier and is present in institute
State the lithium metal in porous carbon materials carrier hole and surface.Quality of the lithium metal in lithium metal-skeleton carbon composite
Degree can be 10%-95% perhaps 20%-70% perhaps 30%-70% or 40%-70%.
In some embodiments, the porous carbon materials include carbon fiber microballoon, porous carbon nanotube microballoon and acetylene black
It is at least one.Carbon fiber microballoon and porous carbon nanotube microballoon are mutually entwined by carbon nanotube or carbon nano-fiber reunites and shape
At with a large amount of nanoscale holes on internal and surface.Such microballoon has approximate solid structure (similar knitting wool unity
Structure), i.e., carbon nanotube or carbon nano-fiber are full of inside microballoon, but between the carbon nanotube or carbon nano-fiber of reunion of entwining
There are nanoscale hole, these holes can be used for accommodating nano carbon particle and lithium metal particle.Acetylene black is to pass through acetylene
Cooling to collect carbon black obtained after gas completely cuts off air progress thermal cracking at high temperature, partial size can be 40-50 nanometers.
In some embodiments, the carbon nanotube microballoon is spherical or near-spherical particle, average diameter can for 1 μm~
100 μm, preferably 1 μm~25 μm；Specific surface area can be 100~1500m2/ g, preferably 150~500m2/g；Institute in microballoon
Pore-size distribution containing hole can be 1~200nm, preferably 1~50nm.
In some embodiments, the carbon nanotube microballoon at least has tiny spherical solid aggregated structure, spherical aggregation
Any one in structure, spherical aggregated structure, porous spherical aggregated structure and bagel shape aggregated structure.
In some embodiments, the carbon nanotube includes multi-walled carbon nanotube, double-walled carbon nano-tube and single
Any one in pipe or two or more combinations, the carbon nanotube optionally pass through surface-functionalized processing.It modifies and is received in carbon
The group of nanotube surface may be selected from but not limited to-COOH ,-OH ,-NH2Equal groups.
In some embodiments, the carbon nanotube microballoon can be dispersed by the way that carbon nanotube to be scattered in be formed in solvent
Then liquid is spray-dried and prepares.For example, preparation method may comprise steps of:
A, carbon nanotube is distributed in dispersion solvent (without surfactant) by ultrasonic treatment, obtains dispersion liquid；
B, the dispersion liquid obtained in step A is sprayed by the nozzle of spray dryer, presetting inlet air temperature and outlet air
Temperature, it is stirring that solution is kept in spray process；
C, cooling, i.e. acquisition carbon nanotube microballoon.
In some embodiments, the solvent use can make carbon nano-tube/carbon nano fabric and nano carbon particle uniform
Dispersion organic and/or inorganic liquid, for example, water, ammonium hydroxide, hydrochloric acid solution, ethyl alcohol, acetone, isopropanol any one or it is more
The combination of kind.
In some embodiments, the solvent can be the mixture of ethyl alcohol and water that volume ratio is 1:10.
In some embodiments, it is 150~250 DEG C that the condition of spray drying, which may include: inlet air temperature, and leaving air temp is
75 DEG C or more, such as 75~150 DEG C, or be 90 DEG C or more；One preferred spray drying condition includes: that inlet air temperature is 190
~210 DEG C, leaving air temp is 90~110 DEG C.
In some embodiments, spray velocity when spray drying can be 1 ml/min to 100 liters/min.
In some embodiments, lithium metal-skeleton carbon composite can be by by molten metal lithium and stephanoporate framework carbon
Material mixing, obtains after cooling.The mixing may include by lithium metal and stephanoporate framework carbon material under heating (for example, about
200 DEG C) it is stirred or immerses stephanoporate framework carbon material in molten metal lithium.Lithium metal-skeleton carbon composite system
It is standby to carry out in an inert atmosphere, such as in the glove box of argon atmosphere (water content < 10ppm, oxygen content < 10ppm).
In some embodiments, the no lithium titanate cathode material is selected from least one of graphite, silicon and lithium titanate.
In some embodiments, the graphite includes pure graphite, the graphite of modification and the dedicated cathode stone of lithium ion battery
Ink powder.The graphite of modification may include surface oxidation reduction, doping other elements or the graphite containing clad.
In some embodiments, the silicon includes the silicon of pure silicon, modification.The silicon of modification may include surface oxidation reduction,
Adulterate other elements or the silicon containing clad.The diameter of silicon particle can be nanoscale or micron order.
In some embodiments, the lithium titanate includes the lithium titanate of pure lithium titanate, modification.The lithium titanate of modification can wrap
Include surface oxidation reduction, doping other elements or the lithium titanate containing clad.The diameter of lithium carbonate can be nanoscale or
Micron order.
In some embodiments, the lithium metal-skeleton carbon composite and the mass ratio of the no lithium titanate cathode material are
1:12 to 1:6.Within the scope of this mass ratio, the lithium metal in lithium metal-skeleton carbon composite can be in battery charge and discharge for the first time
Lithium consumed by SEI layers of negative terminal surface formation is sufficiently replenished in electric process, and is suitable in cost.
In some embodiments, the negative electrode material also includes binder.The binder is for making lithium metal-skeleton carbon
Composite material and without lithium titanate cathode material and their stable bonds between substrate such as metal collector.
In some embodiments, the binder includes polystyrene, butadiene-styrene rubber, at least one in Kynoar
Kind.
In some embodiments, the negative electrode material may include conductive agent, can not also include conductive agent, the conduction
Agent is at least one of acetylene black, Super P.
In some embodiments, the modification further includes metal collector without cathode of lithium pole piece, the negative electrode material load
In in the metal collector.
In some embodiments, the metal collector includes copper foil.The thickness of copper foil can be about 9 μm (+/- 3 μm).
Another aspect of the present invention provides a kind of method of the modification for preparing lithium ion battery without cathode of lithium, the method
Including: will be containing whether there is or not the negative electrode material slurries of lithium titanate cathode material and lithium metal-skeleton carbon composite mixture to be coated on gold
Belong on collector, forms cathode pole piece.
In some embodiments, the negative electrode material slurry includes no lithium titanate cathode material, lithium metal-skeleton carbon composite wood
Material, binder, dispersing agent and optional conductive agent.
In some embodiments, the dispersing agent in paraxylene, tetrahydrofuran, N-Methyl pyrrolidone at least
It is a kind of.
About " no lithium titanate cathode material ", " lithium metal-skeleton carbon composite ", " binder " and " conductive agent " and they
Dosage, referring to above-mentioned associated description.
In some embodiments, preparation method of the modified lithium ion battery without cathode of lithium may include walking in detail below
It is rapid:
1. being coated with preparation method
It (1) will (mixing can be without lithium titanate cathode material, lithium metal-skeleton carbon composite, binder and dispersant
Stirring is lower to be carried out, and mixing speed can be 200-300 revs/min, and the time can be 10 hours or more), form negative electrode material slurry
Material；
(2) by the negative electrode material slurry coating of step (1) preparation (coating method may include blade coating, spin coating, spraying etc.,
Coating layer thickness can be 100-1000 microns, for example, about 500 microns) in metal collector, such as copper foil；
(3) the resulting metal collector for being coated with negative electrode material slurry of drying steps (2) forms cathode pole piece.
2. pressure bonding method
(1) lithium metal-skeleton carbon composite is dispersed in had been coated with without on cathode of lithium pole piece.
(2) applying pressure makes lithium metal-skeleton carbon composite pressure be compound in no cathode of lithium pole piece.
In some embodiments, pressure bonding is carried out by roll squeezer or static pressure machine, and pressure limit can be 10MPa-
100MPa。
In some embodiments, the content of the lithium carbon composite of unit area dispersion is that unit area graphite contains in pole piece
The 2%-20% of amount.
Another aspect of the present invention provides a kind of lithium ion battery, and it includes above-mentioned modifications without cathode of lithium.
In some embodiments, the lithium battery includes primary, serondary lithium battery.
Another aspect of the present invention provides a kind of method for improving for the first time cycle efficieny of the lithium ion battery without cathode of lithium,
The method includes lithium metal-skeleton carbon composite, the lithium metal-skeleton carbon composite wood are combined in no lithium titanate cathode material
The content of material is the 2%-20% of negative electrode active material quality by percentage to the quality.
About " no lithium titanate cathode material " and " lithium metal-skeleton carbon composite ", referring to above-mentioned associated description.
Following detailed description is intended to illustratively and in non-limiting manner illustrate the disclosure.
Specific embodiment 1 is a kind of modification of lithium ion battery without cathode of lithium, wherein the modification without cathode of lithium in addition to
Outside without lithium titanate cathode material, also contain lithium metal-skeleton carbon composite, the lithium metal-skeleton carbon composite content with
Mass percent is calculated as the 2%-20% of negative electrode active material quality.
Specific embodiment 2 is the modification according to specific embodiment 1 without cathode of lithium, wherein the lithium metal-bone
Frame carbon composite includes porous carbon materials carrier and is present in the porous carbon materials carrier hole and the metal on surface
Lithium.
Specific embodiment 3 is the modification according to specific embodiment 1 or 2 without cathode of lithium, wherein the lithium metal-
The content of lithium metal is 10%-95% by percentage to the quality in skeleton carbon composite.
Specific embodiment 4 is the modification according to specific embodiment 2 or 3 without cathode of lithium, wherein the porous carbon
Material includes at least one of carbon fiber microballoon, porous carbon nanotube microballoon and acetylene black.
Specific embodiment 5 is the modification according to specific embodiment 4 without cathode of lithium, wherein the porous carbon nanometer
Pipe microballoon is mutually to be entwined reunite and is formed, have the microballoon of nanoscale hole on internal and surface by carbon nanotube, micro-
Spherolite diameter is 1-100 microns.
Specific embodiment 6 is the modification according to specific embodiment 5 without cathode of lithium, wherein the carbon nanotube is micro-
The specific surface area of ball is 100~1500m2/g；
And/or the aperture of hole contained by the carbon nanotube microballoon is 1~200nm；
And/or the carbon nanotube microballoon at least has tiny spherical solid aggregated structure, spherical aggregated structure, class ball
Any one in shape aggregated structure, porous spherical aggregated structure and bagel shape aggregated structure；
And/or the carbon nanotube includes any in multi-walled carbon nanotube, double-walled carbon nano-tube and single-walled carbon nanotube
A combination of one or more, the carbon nanotube optionally pass through surface-functionalized processing.
Specific embodiment 7 is the modification according to any one of specific embodiment 1-6 without cathode of lithium, wherein described
No cathode of lithium active material is selected from least one of graphite, silicon and lithium titanate.
Specific embodiment 8 is the modification according to specific embodiment 7 without cathode of lithium, wherein the graphite includes pure
Graphite or the graphite of modification.
Specific embodiment 9 is the modification according to specific embodiment 7 without cathode of lithium, wherein the graphite of the modification
Including surface oxidation reduction, doping other elements or contain the graphite of clad.
Specific embodiment 10 is the modification according to any one of specific embodiment 7-9 without cathode of lithium, wherein institute
It states lithium metal-skeleton carbon composite and the mass ratio without lithium titanate cathode material is 1:12 to 1:6.
Specific embodiment 11 is the modification according to any one of specific embodiment 1-10 without cathode of lithium, wherein institute
Stating negative electrode material also includes binder.
Specific embodiment 12 is the modification according to specific embodiment 11 without cathode of lithium, wherein the binder packet
Include at least one of polystyrene, butadiene-styrene rubber, Kynoar.
Specific embodiment 13 is the modification according to any one of specific embodiment 1-12 without cathode of lithium, wherein institute
It further includes metal collector that modification, which is stated, without cathode of lithium, and the negative electrode material is carried in the metal collector.
Specific embodiment 14 is the modification according to specific embodiment 13 without cathode of lithium, wherein the metal afflux
Body includes copper foil.
Specific embodiment 15 is a kind of to prepare modification described in any one of specific embodiment 1-14 without cathode of lithium
Method, the method comprise the steps that
It will be containing whether there is or not the negative electrode material slurries of lithium titanate cathode material and lithium metal-skeleton carbon composite mixture to be coated on
In metal collector, cathode pole piece is formed；Or lithium metal-skeleton carbon composite is dispersed in coated no cathode of lithium pole
On piece is simultaneously compound in no cathode of lithium pole piece in a manner of pressure bonding.
Specific embodiment 16 is the method according to specific embodiment 15, wherein the negative electrode material slurry includes
Without lithium titanate cathode material, lithium metal-skeleton carbon composite, binder, dispersing agent and optional conductive agent.
Specific embodiment 17 is the method according to specific embodiment 16, wherein the dispersing agent is selected to diformazan
At least one of benzene, tetrahydrofuran, N-Methyl pyrrolidone.
Specific embodiment 18 is a kind of lithium ion battery, wherein the lithium ion battery includes specific embodiment 1-14
Any one of described in modification without cathode of lithium.
Specific embodiment 19 is the lithium ion battery according to specific embodiment 18, wherein the lithium battery pack includes
Disposable lithium-battery, serondary lithium battery.
Specific embodiment 20 is a kind of method for improving for the first time cycle efficieny of the lithium ion battery without cathode of lithium, wherein institute
The method of stating, which is included in no lithium titanate cathode material, combines lithium metal-skeleton carbon composite, the lithium metal-skeleton carbon composite
Content be by percentage to the quality negative electrode active material quality 2%-20%.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Postscript, used various products structural parameters, various reaction partners and technique item among following examples
Part is more typical example, but is verified by inventor's a large number of experiments, in the other different structures of those listed above
Parameter, other types of reaction partner and other process conditions are also applicable, and also equal attainable cost invention is claimed
Technical effect.
Embodiment 1
1. lithium-carbon skeleton composite material preparation
2g is added without any chemically treated multi-walled carbon nanotube (Shanghai Peng Xin new material Science and Technology Ltd.) first
Enter 200mL deionized water, it is rear that 20mL dehydrated alcohol is added.Sealing stirring, 130W ultrasonic probe are ultrasonically treated 5 hours, make sample
It is evenly dispersed.After spray dryer is added in sample.Inlet air temperature is set as 200 DEG C, and leaving air temp is set in 150 DEG C,
Atomisation pressure is set as 40MPa, and sample volume is set as 500mL/h, obtains porous carbon nanotube micro-sphere material after dry.To micro-
Ball carries out nitrogen adsorption desorption test, and microballoon specific surface area is 151m2/ g, average pore size 18.7nm.
It weighs 100mg Battery grade lithium metal (energy lithium industry in Tianjin) and the porous carbon nanotube micro-sphere material of 100mg is placed in not
It becomes rusty in steel heater, is heated to 220 DEG C, stirring continues 6 minutes, mixing terminates, and is cooled to room temperature.The process is protected in argon gas
Glove box in carry out (water oxygen content be not higher than 10ppm).Obtain the porous carbon nanotube microballoon composite material (lithium-bone of lithium metal-
Frame carbon composite is a kind of).Gained lithium metal-porous carbon nanotube microballoon composite material specific capacity is 1600mAh/g.
2. prepared by slurry
2.1 graphite slurry
According to artificial graphite (Shenzhen section is brilliant): acetylene black (Alfa Aesar company, similarly hereinafter): (polystyrene (melt index
6g/min (200 DEG C/5kg), Sigma-Aldrich China, similarly hereinafter)+butadiene-styrene rubber (molecular weight is 2,000,000) Sigma-
Aldrich China, similarly hereinafter)=450mg:50mg:50mg weighs various substances, be added paraxylene (it is super dry, water content <
50ppm, Shanghai Aladdin biochemical technology limited liability company think, similarly hereinafter) 1.5 milliliters.Magnetic stirrer over night (is greater than 10 hours),
Stirring is 200-300 revs/min several times.
The slurry of 2.2 lithiums-carbon skeleton composite material benefit lithium
According to artificial graphite: lithium-carbon skeleton composite material (synthesizes) in synthetic example 1: acetylene black: (polystyrene+fourth
Benzene rubber)=415mg:35mg:50mg:50mg weighs various substances, it is added 1.5 milliliters of paraxylene.Magnetic stirrer over night is (big
In 10 hours), stirring is 200-300 revs/min several times.
3. coating
By the above two slurry stirred evenly, is scratched on copper foil (with a thickness of 12 microns), scraped by the way of blade coating
Knife is with a thickness of 500 microns.
4. drying
Pole piece in above-mentioned 2 is dried into (about 10 hours) in 60 C overnights, so that paraxylene volatilizees completely.
5. battery assembly
Above two pole piece is struck out electrode wafer that diameter is 15 millimeters as the negative electrode material of lithium battery by 5.1, electric
Solve the LiPF that liquid is 1mol/L6Three component mixed solvent EC:DMC:EMC=1:1:1 (v/v/v, China fir China fir electrolyte, similarly hereinafter),
Polypropylene microporous film be diaphragm (Celgard 2400, similarly hereinafter), with lithium metal (16 millimeters of diameter, 400 microns of thickness, Shenzhen
Than source Electronics Co., Ltd., similarly hereinafter) for electrode assembling battery (button cell, CR2025, Shenzhen than source Electronics Co., Ltd.,
Similarly hereinafter).
2.2-5.1 process carries out in the glove box full of argon gas, and wherein water oxygen content is not higher than 10ppm.
Simulated battery in 5.2 pair 5.1 carries out constant current charge-discharge, charging/discharging voltage range: 0.01-1V, charge and discharge electricity electricity
Stream is 0.1C.
Fig. 1 shows electric discharge-charging curve for the first time of graphite cathode, in 0.7V in the discharge process for the first time of graphite cathode
It is the platform of graphite cathode surface production SEI film that, which there is a platform in left and right, and the coulombic efficiency of the first charge-discharge of graphite cathode is
81%.
Fig. 2, which is shown, mends the graphite cathode of lithium electric discharge-charging curve for the first time using lithium metal-skeleton carbon composite.It mends
0.7V or so abolition of plateau after lithium, and compare and discharge for the first time and the capacity that charges can obtain the coulombic efficiency of first charge-discharge and be
99%.It can be seen that being blended by lithium metal-skeleton carbon composite with graphite material, the head of graphite cathode is effectively increased
Effect.
Fig. 3 is shown graphite cathode and is mended the graphite cathode charge and discharge cycles of lithium using lithium metal-skeleton carbon composite
Curve graph.It can be seen that mending the graphite cathode charge and discharge cycles curve of lithium using lithium metal-skeleton carbon composite in figure, it is seen that
It is 99% or more that it, which recycles coulombic efficiency, and capacity retention ratio is 80% after 50 circulations.
Embodiment 2
1. prepared by slurry
1.1 silicium cathode slurries
Silicon (Shenzhen section is brilliant): acetylene black (Alfa Aesar company): (polystyrene (melt index 6g/min (200 DEG C/
5kg))+butadiene-styrene rubber (molecular weight be 2,000,000))=450mg:50mg:50mg weighs various substances, it is (super that paraxylene is added
Dry, water content < 50ppm) 1.5 milliliters.Magnetic stirrer over night (is greater than 10 hours), and stirring is 200-300 revs/min several times.
The slurry of 1.2 lithiums-carbon skeleton composite material benefit lithium
Silicon: lithium-carbon skeleton composite material (the preparation method is the same as that of Example 1): acetylene black: (polystyrene+butadiene-styrene rubber)=
350mg:100mg:50mg:50mg weighs various substances, is added 1.5 milliliters of paraxylene.Magnetic stirrer over night (it is small to be greater than 10
When), stirring is 200-300 revs/min several times.
2. coating
By the above two slurry stirred evenly, is scratched on copper foil (with a thickness of 12 microns), scraped by the way of blade coating
Knife is with a thickness of 500 microns.
3. drying
Pole piece in above-mentioned 2 is dried into (about 10 hours) in 60 C overnights, so that paraxylene volatilizees completely.
4. battery assembly
4.1 above two pole piece is struck out diameter is 15 millimeters of electrode wafer as the negative electrode material of lithium battery.Electricity
Solve the LiPF that liquid is 1mol/L6Three component mixed solvent EC:DMC:EMC=1:1:1 (volume ratio v/v/v), polypropylene microporous
Film is diaphragm, is assembled into simulated battery by anode of lithium metal.
The above process carries out in the glove box full of argon gas, and wherein water oxygen content is not higher than 10ppm.
Simulated battery in 4.2 pair 4.1 carries out constant current charge-discharge, charging/discharging voltage range: 0.01-1V, charge and discharge electricity electricity
Stream is 0.1C.
Fig. 4 is shown silicium cathode and is mended silicium cathode electric discharge for the first time-charging song of lithium using lithium metal-skeleton carbon composite
Line.The coulombic efficiency that the capacity that comparison discharges and charges for the first time can obtain first charge-discharge is 98%, and the silicium cathode without mixing lithium
First charge discharge efficiency is only 83%.It can be seen that being blended by lithium metal-skeleton carbon composite with silicium cathode material, effectively increase
The first effect of silicium cathode.
Embodiment 3
Graphite cathode pole piece (take in the fresh new energy Co., Ltd in Suzhou, similarly hereinafter), wherein content of graphite is 90%.
Lithium-carbon skeleton composite material preparation is as described in example 1 above.
Prepared lithium-carbon skeleton composite material is dispersed on graphite pole piece, lithium every square centimeter-carbon skeleton composite material
Quality be 1.0mg.Using roll squeezer, roll-in lithium-carbon skeleton composite material and graphite pole piece, so that lithium-carbon skeleton composite wood
Material is securely embedded into cathode pole piece, pressure applied 30MPa, and cathode pole piece is made.
Battery assembly and test, as described in example 1 above.
Fig. 5 is the cathode pole piece first charge-discharge curve that lithium is mended using above-mentioned method, it can be seen that due to lithium-carbon skeleton
The addition of composite material, the potential plateau (0.7V or so) that negative discharge forms SEI layers in the process disappears, and coulombic efficiency for the first time
It is 85%, illustrates that the addition of lithium-carbon skeleton composite material plays the purpose that supplement forms SEI consumption lithium.
Fig. 6 is that the capacity of the battery keeps curve.It can be seen that 70 circulations of the battery can keep 95% or more
Coulombic efficiency.
It should be appreciated that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not intended to limit the invention, it is all at this
Made any modifications, equivalent replacements, and improvements etc., should be included in protection model of the invention within the spirit and principle of invention
Within enclosing.
Claims (10)
1. a kind of modification of lithium ion battery is without cathode of lithium, it is characterised in that the modification is without cathode of lithium in addition to no lithium titanate cathode material
Outside, also contain lithium metal-skeleton carbon composite, the lithium metal-skeleton carbon composite content is by percentage to the quality
For the 2%-20% of no cathode of lithium active material quality.
2. modification according to claim 1 is without cathode of lithium, it is characterised in that the lithium metal-skeleton carbon composite includes
Porous carbon materials carrier and the lithium metal being present in the porous carbon materials carrier hole and surface.
3. modification according to claim 2 is without cathode of lithium, it is characterised in that the porous carbon materials include carbon fiber microballoon,
At least one of porous carbon nanotube microballoon and acetylene black.
4. modification according to claim 2 is without cathode of lithium, it is characterised in that golden in the lithium metal-skeleton carbon composite
The content for belonging to lithium is 10%-95% by percentage to the quality.
5. modification according to claim 1 is without cathode of lithium, it is characterised in that the no cathode of lithium active material be selected from graphite,
At least one of silicon and lithium titanate.
6. modification according to claim 1 is without cathode of lithium, it is characterised in that the modification further includes metal collection without cathode of lithium
Fluid, the negative electrode material are carried in the metal collector.
7. a kind of prepare method of the modification of any of claims 1-6 without cathode of lithium, it is characterised in that the method
Include:
It will be containing whether there is or not the negative electrode material slurries of lithium titanate cathode material and lithium metal-skeleton carbon composite mixture to be coated on metal
On collector, cathode pole piece is formed；
Or lithium metal-skeleton carbon composite is dispersed on coated no cathode of lithium pole piece and is answered in a manner of pressure bonding
Together in no cathode of lithium pole piece.
8. according to the method described in claim 7, it is characterized in that the negative electrode material slurry includes no lithium titanate cathode material, metal
Lithium-skeleton carbon composite, binder, dispersing agent and optional conductive agent.
9. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes of any of claims 1-6 changes
Property is without cathode of lithium.
10. a kind of method for improving for the first time cycle efficieny of the lithium ion battery without cathode of lithium, it is characterised in that the method includes
Lithium metal-skeleton carbon composite is combined in no lithium titanate cathode material, the lithium metal-skeleton carbon composite content is with matter
Percentages are measured as the 2%-20% of no cathode of lithium active material quality.
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| PCT/CN2017/105674 WO2019019410A1 (en) | 2017-07-26 | 2017-10-11 | Modified lithium-free anode, method for preparing same, and lithium-ion battery comprising same |
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