CN107768733B - A kind of lithium battery and preparation method thereof - Google Patents
A kind of lithium battery and preparation method thereof Download PDFInfo
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- CN107768733B CN107768733B CN201710954806.8A CN201710954806A CN107768733B CN 107768733 B CN107768733 B CN 107768733B CN 201710954806 A CN201710954806 A CN 201710954806A CN 107768733 B CN107768733 B CN 107768733B
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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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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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
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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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- 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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- 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
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Abstract
The present invention relates to technical field of lithium batteries, more particularly to a kind of lithium battery and preparation method thereof, the lithium battery, including anode, cathode, diaphragm and electrolyte, the anode is including plus plate current-collecting body and coated in the positive electrode on the plus plate current-collecting body, wherein, the plus plate current-collecting body is graphitization alkene layer aluminium foil；The cathode includes negative current collector and coated in the negative electrode material on the negative current collector, wherein the negative current collector is graphitization alkene layer copper foil.Graphitization alkene layer aluminium foil and graphitization alkene layer copper foil is respectively adopted as plus plate current-collecting body and negative current collector in the present invention, not only increase the electric conductivity of plus plate current-collecting body and negative current collector, graphite ene coatings can also avoid the oxidation of metal, to improve the efficiency for charge-discharge and cycle performance of lithium battery.
Description
Technical field
The present invention relates to technical field of lithium batteries, and in particular, to a kind of lithium battery and preparation method thereof.
Background technique
Lithium ion battery passes through the development of many years, has become the new-energy automobile power source being most widely used instantly,
It is widely used in electric vehicle field, such as hybrid-power bus, pure electric bus.And in lithium ion battery
Use process in, efficiency for charge-discharge problem is the key point of capacity usage ratio and is concerned and current techniques personnel grind
One of major issue studied carefully.Internal resistance is to influence one of efficiency for charge-discharge and the key factor of cycle life.Big internal resistance meeting so that
Battery specific energy sharp fall in high-power output, so that starting performance be made to be deteriorated；Increase battery temperature, safety by
To threat；And shorten the cycle life of battery.
Currently, LiFePO4 and nickel-cobalt-manganese ternary material are two kinds of anode material for lithium-ion batteries of greatest concern.Phosphoric acid
Iron lithium anode material is because it than nickel-cobalt-manganese ternary material has higher thermal decomposition temperature, and shows in charge and discharge process
Better thermodynamic stability, it is considered to be the anode material for lithium-ion batteries of more secure and reliable.And in LiFePO4 structure
Polyanion ensure that its structural stability during repeated charge；LiFePO4And FePO4Structure is similar, volume phase
Closely, therefore in charge and discharge process structure and volume change are small, so that LiFePO4 has excellent cycle performance.But it is limited to material
The theoretical specific capacity of material itself low conductivity and 170mAh/g, so that it shows slightly in aspect of performance such as Energy Efficiency Ratio, energy densities
It is insufficient.Therefore, the Energy Efficiency Ratio and energy density for improving ferric phosphate lithium cell are the key that it is promoted further to apply.
Summary of the invention
Of the existing technology in order to overcome the problems, such as, an object of the present invention is to provide a kind of lithium battery, the lithium electricity
Pond has good Energy Efficiency Ratio.
The second object of the present invention is to provide a kind of preparation method of lithium battery.
It was found by the inventors of the present invention that the electric conductivity of lithium battery anode and cathode be influence charging and discharging lithium battery efficiency because
One of element, charging and discharging lithium battery efficiency is improved with the raising of the electric conductivity of lithium battery anode, cathode of lithium battery, and collector is
One of an important factor for influencing anode and negative conductive, and traditional metal collector makes and uses process in lithium battery
In, it is easy to happen oxidation, leads to the reduction of its electric conductivity, to influence the charge-discharge performance of lithium battery.
To achieve the goals above, the present invention provides a kind of lithium battery, including anode, cathode, diaphragm and electrolyte, described
Anode is including plus plate current-collecting body and coated in the positive electrode on the plus plate current-collecting body, wherein the plus plate current-collecting body is to apply
Graphene layer aluminium foil；
The cathode includes negative current collector and coated in the negative electrode material on the negative current collector, wherein described negative
Pole collector is graphitization alkene layer copper foil.
The present invention also provides a kind of preparation methods of lithium battery, comprising the following steps:
(1) positive preparation；
(2) preparation of cathode；
(3) electrolyte will be injected after the positive electrode, the negative electrode and the separator coiling and molding, inert gas is then filled with into lithium battery,
Be 0.3~3MPa to pressure, then by lithium battery at 20~35 DEG C upright 6-24h, then the upright 6-24h at 40-55 DEG C, so
After be evacuated to pressure be -0.08~-0.05MPa under seal after obtain lithium battery.
Through the above technical solutions, the present invention has following technical effect that
(1) graphitization alkene layer aluminium foil and graphitization alkene layer copper foil is respectively adopted as plus plate current-collecting body and cathode collection in the present invention
Fluid not only increases the electric conductivity of plus plate current-collecting body and negative current collector, and graphite ene coatings can also avoid the oxidation of metal,
To improve the efficiency for charge-discharge and cycle performance of lithium battery；
(2) in battery preparation, in the impregnation process of electrolyte, by injecting inert gas, inside battery is improved
Pressure enables electrode slice to be infiltrated completely by electrolyte, to improve the biography of ion and electronics in the charge and discharge process in later period
Defeated efficiency improves the Energy Efficiency Ratio of lithium battery.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 be in the embodiment of the present invention 1 lithium battery temperature be 25 DEG C, discharge-rate be 0.5C under discharge curve；
Fig. 2 is that lithium battery in temperature is 25 DEG C in the embodiment of the present invention 1, and discharge-rate is that the cycle performance under 0.5C is bent
Line；
Fig. 3 be in the embodiment of the present invention 1 lithium battery temperature be -20 DEG C, discharge-rate be 0.5C under discharge curve；
Fig. 4 be in the embodiment of the present invention 1 lithium battery temperature be 55 DEG C, discharge-rate be 0.5C under discharge curve.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In order to optimize the efficiency for charge-discharge of lithium battery, the present invention provides a kind of lithium battery, including anode, cathode, diaphragm and
Electrolyte, the anode is including plus plate current-collecting body and coated in the positive electrode on the plus plate current-collecting body, wherein the anode
Collector is graphitization alkene layer aluminium foil；
The cathode includes negative current collector and coated in the negative electrode material on the negative current collector, wherein described negative
Pole collector is graphitization alkene layer copper foil.
In the present invention, using graphitization alkene layer aluminium foil and graphitization alkene layer copper foil as plus plate current-collecting body and negative pole currect collecting
Body not only increases the electric conductivity of plus plate current-collecting body and negative current collector, and graphite ene coatings can also avoid the oxidation of metal, from
And improve the efficiency for charge-discharge and cycle performance of lithium battery.
According to the present invention, the graphitization alkene layer aluminium foil includes that aluminium foil and the first graphene coated in aluminium foil surface apply
Layer, in order to optimize the electric conductivity of graphitization alkene layer aluminium foil, under preferable case, the aluminium foil with a thickness of 14-20 μm；Described first
Graphite ene coatings with a thickness of 1-3 μm.
According to the present invention, the graphitization alkene layer copper foil includes that copper foil and the second graphene coated in copper foil surface apply
Layer, in order to optimize the electric conductivity of graphitization alkene layer copper foil, under preferable case, the copper foil with a thickness of 7-11 μm；Described second
Graphite ene coatings with a thickness of 1-3 μm.
According to the present invention, the electrolyte is the mixed solution of electrolyte lithium salt and nonaqueous solvents, the nonaqueous solvents packet
Include ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, and the ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate
Volume ratio is 1:(0.8~1.2): (0.8~1.2), further preferably 1:1:1.In order to which battery is formed in formation process
Stablize fine and close SEI film, reduces the internal resistance of battery；Under preferable case, coalescing agent, the film forming are also contained in the electrolyte
Auxiliary agent is selected from least one of vinylene carbonate, propylene sulfite and ethylene sulfite, it is further preferred that with institute
On the basis of the total weight for stating electrolyte, the content of the coalescing agent is 0.5~3 weight %.
According to the present invention, in order to improve the cycle efficieny of battery, the cycle life of battery is improved, it is described under preferable case
Also containing glycol dimethyl ether in electrolyte, the content of the glycol dimethyl ether is 0.5~3 weight %,
According to the present invention, the nonaqueous electrolytic solution of this field routine can be used in the electrolyte.Such as electrolyte lithium salt choosing
From lithium hexafluoro phosphate (LiPF6), lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and fluorohydrocarbon base sulphur
One or more of sour lithium, the concentration of electrolyte is generally 1~1.3mol/L in electrolyte.
According to the present invention, the positive electrode includes positive electrode active materials, conductive agent, binder, the positive-active material
Material includes carbon-coated LiFePO 4 for lithium ion batteries, and the volume average particle size distribution D50 of the carbon-coated LiFePO 4 for lithium ion batteries is 7~15 μm, vibration density
Spend 0.8~1.8g/cm3, specific surface area be 7~22m2/g。
Using the carbon-coated LiFePO 4 for lithium ion batteries positive electrode with high conductivity in the present invention, it compensates for LiFePO4 itself
The insufficient defect of electric conductivity, is conducive to the performance of material capacity, and reduces the contact resistance of battery, by controlling carbon coating phosphoric acid
The porosity of anode can be improved in the partial size and pole piece compaction density of iron lithium, increases the positive imbibition to electrolyte, guarantor's liquid energy
Power reduces polarization of the battery in charge and discharge process, improves the efficiency for charge-discharge and cycle life of lithium battery.
According to the present invention, the dosage of each substance in positive electrode can be adjusted according to actual needs, for example, at this
In a kind of more preferably embodiment of invention, in order to further increase lithium iron phosphate dynamic battery obtained at low temperature
Cycle performance, on the basis of the total weight of positive electrode, the content of the positive electrode active materials is 94-97.7 weight %, conduction
The content of agent is 0.8~3 weight %, the content of binder is 1.0~3.5 weight %.
According to the present invention, the conductive agent can be type commonly used in the art, for example, the conductive agent can select
From carbon black, electrically conductive graphite, carbon nanotube, graphene and carbon nano-fiber etc., under preferable case, the conductive agent is selected from acetylene
Black, conductive black, graphite is dilute and carbon nanotube at least two.
According to the present invention, the binder can be type commonly used in the art, for example, the binder can select
From polyvinyl alcohol, polyvinylidene fluoride, sodium carboxymethylcellulose, polyolefins binder and Viton etc., under preferable case,
The binder is polyvinylidene fluoride.
According to the present invention, in order to advanced optimize the discharging efficiency of lithium battery, under preferable case, the lithium battery anode
Compacted density is 2~2.6g/cm3, further preferably 2.2~2.4g/cm3。
According to the present invention, in order to advanced optimize the discharging efficiency of lithium battery, under preferable case, the lithium battery anode
Surface density is 150~168g/cm2, further preferably 155~161g/cm2。
According to the present invention, the negative electrode material includes negative electrode active material, conductive agent, binder, the negative electrode active material
Material includes artificial graphite.The space utilization rate of artificial graphite can be improved by improving tap density, improve the space of lithium battery
Utilization rate, but if its tap density and compacted density are excessively high, it is obvious that cathode rebound is not only resulted in, so that assembling coefficient mistake
Height causes into shell difficulty is big or later period battery core bulging, and there are security risk etc., the brittleness for also resulting in cathode becomes larger, and is winding
Pole piece is broken when Battery Pole Core, cannot not only improve the low-temperature circulating performance of battery, even more so that the preparation of battery
It is unable to complete.
Under preferable case, the tap density of the artificial graphite is 0.8~1.2g/cm3, 2~5m of specific surface area2/g.Root
According to the present invention, the dosage of each substance in negative electrode material can be adjusted according to actual needs, for example, in one kind of the invention
More preferably in embodiment, in order to further increase the cycle performance of lithium iron phosphate dynamic battery at low temperature obtained,
On the basis of the total weight of negative electrode material, the content of the negative electrode active material is 94-97 weight %, the content of conductive agent is
0.4~1.6 weight %, binder content be 2.5~5 weight %.
According to the present invention, the conductive agent can be type commonly used in the art, for example, the conductive agent can select
At least two from carbon nanotube, acetylene black, conductive black, graphite agent KS.
According to the present invention, the binder can be type commonly used in the art, for example, the binder can select
From polyvinyl alcohol, polytetrafluoroethylene (PTFE), carboxymethyl cellulose, polyolefins binder, butadiene-styrene rubber and Viton etc., preferably feelings
Under condition, the binder is carboxymethyl cellulose.
According to the present invention, in order to advanced optimize the discharging efficiency of lithium battery, under preferable case, the cathode of lithium battery
Compacted density is 1.35~1.86g/cm3, further preferably 1.5~1.7g/cm3。
According to the present invention, in order to advanced optimize the discharging efficiency of lithium battery, under preferable case, the cathode of lithium battery
Surface density is 63~82g/cm2, further preferably 67~80g/cm2。
The present invention also provides a kind of preparation methods of lithium battery, comprising the following steps:
(1) positive preparation；
(2) preparation of cathode；
(3) electrolyte will be injected after the positive electrode, the negative electrode and the separator coiling and molding, inert gas is then filled with into lithium battery,
Be 0.3~3MPa to pressure, then by lithium battery at 20~35 DEG C upright 6-24h, then the upright 6-24h at 40-55 DEG C, so
After be evacuated to pressure be -0.08~-0.05MPa under seal after obtain lithium battery.
According to the present invention, in battery preparation, in the impregnation process of electrolyte, by injecting inert gas, electricity is improved
Pressure inside pond enables electrode slice to be infiltrated completely by electrolyte, thus in the charge and discharge process in later period, improve ion and
The efficiency of transmission of electronics improves the Energy Efficiency Ratio of lithium battery.
According to the present invention, the preparation method of the anode can be method commonly used in the art, such as can be with are as follows:
A, under vacuum conditions, positive electrode binder and N-Methyl pyrrolidone are uniformly mixed, obtaining mass concentration is
The anode of 5%-10% closes slurry glue；
B, under vacuum conditions, temperature be that anode is closed into slurry glue and positive conductive agent, positive-active material at 20-50 DEG C
Material stirring is to be made anode sizing agent；
C, anode sizing agent is coated on at least one side of plus plate current-collecting body, dries, rolls, slitting, film-making, obtaining lithium battery just
Pole.
According to the present invention, the preparation method of the anode can be method commonly used in the art, such as can be with are as follows:
A, under vacuum conditions, positive electrode binder and N-Methyl pyrrolidone are uniformly mixed, obtaining mass concentration is
The anode of 1.5%-1.8% closes slurry glue；
B, under vacuum conditions, temperature be that anode is closed into slurry glue and positive conductive agent, positive-active material at 20-50 DEG C
Material stirring is to be made anode sizing agent；
C, anode sizing agent is coated on at least one side of plus plate current-collecting body, dries, rolls, slitting, film-making, obtaining lithium battery just
Pole.
According to the preparation method of lithium battery provided by the invention, the coiling and molding technique, electrolyte injection technology and envelope
Filling moulding process can be known to those skilled in the art, and details are not described herein by the present invention.
The present invention will be described in detail by way of examples below, and conductive black is close purchased from Switzerland spy in following embodiment
Height, model SP；
Electrically conductive graphite is purchased from Switzerland Te Migao, model KS6；
N-Methyl pyrrolidone (NMP) is purchased from Nanjing Jin Long Chemical Co., Ltd.；
Carbon coating type LiFePO 4 material reaches new energy Co., Ltd, model HSD-1 purchased from Hai Si；
Artificial graphite is purchased from Shenzhen Bei Terui new energy materials limited liability company, model S360；
Graphitization alkene layer aluminium foil, graphitization alkene layer copper foil are macro purchased from Dongguan Hua Zhiwei；
PVDF is in harmony (Shanghai) International Trading Company Ltd purchased from friend, model 5130；
Carboxymethyl cellulose (cmc) is purchased from Hercules chemical industry (Jiangmen) Co., Ltd, model BVH8；,
LiPF6, vinylene carbonate, propylene sulfite, ethylene sulfite, glycol dimethyl ether, ethylene carbonate
(EC), methyl ethyl carbonate (EMC), dimethyl carbonate (DMC) are purchased from Guangzhou Tianci Advanced Materials Co., Ltd；
Embodiment 1
(1) anode preparation
1.6kg PVDF is dissolved in 21kg NMP, the PVDF glue that mass concentration is 7% is obtained；By 96.8kg carbon packet
Covering LiFePO4, (it is 10 μm, tap density 1.2g/cm that volume average particle size, which is distributed D50,3, specific surface area 15m2/ g), 1kg leads
Electro-graphitic, 0.6kg graphene and above-mentioned PVDF glue are stirred evenly under conditions of 40 DEG C of vacuum degree≤- 0.08MPa to be made
Anode sizing agent；
By anode sizing agent be coated on a thickness of 20 μm graphitization alkene layer aluminium foil tow sides (graphene layer be 2 μm+thickness
Aluminium foil for 16 μm), then 120 DEG C drying, under the pressure of 1.6MPa after roll-in on cutting machine cutting obtain having a size of
The anode of 2350mm × 180mm × 20 μm, obtaining surface density is 161g/m2, compacted density 2.3g/cm3Anode.
(2) prepared by cathode
3kg CMC is dissolved in 173kg deionized water, the CMC glue that mass concentration is 1.7% is obtained；By 95kg people
Make graphite (tap density 1.02g/cm3, specific surface area 3.2m2/ g), 0.5kg electrically conductive graphite, 0.5kg carbon nanotube with it is above-mentioned
CMC glue is stirred evenly under conditions of 20 DEG C of vacuum degree≤- 0.08MPa negative electrode slurry is made；
By negative electrode slurry be coated on a thickness of 13 μm graphitization alkene layer copper foil tow sides (graphene layer be 2 μm+thickness
Copper foil for 9 μm), then 120 DEG C drying, under the pressure of 1.6MPa after roll-in on cutting machine cutting obtain having a size of
The cathode of 2480mm × 184mm × 13 μm, obtaining surface density is 75g/m2, compacted density 1.55g/m3。
(3) by LiPF6With ethylene sulfite, glycol dimethyl ether, ethylene carbonate (EC), methyl ethyl carbonate (EMC)
LiPF is configured to dimethyl carbonate (DMC)6Solution that concentration is 1.3mol/L (wherein, the weight ratio of EC, EMC and DMC are 1:
1:1), on the basis of the total weight of electrolyte, wherein the content of propylene sulfite is the total weight 2% of electrolyte, ethylene glycol
The content of dimethyl ether propylene sulfite is the total weight 2% of electrolyte.
The cathode that anode, membrane layer polyethylene (PE), (2) that (1) obtains obtain successively is wound into up- coiler stacking
The electrode group of scroll is fitted into the square aluminum hull that length is respectively 115mm, 36mm, 220mm in such a way that 4 battery cores are in parallel,
Again by aluminum hull cover board and aluminum hull laser welding, electrolyte is injected, inert gas is then filled with into lithium battery, until pressure is
1.5MPa, by lithium battery at 25 DEG C upright 12h, then the upright 12h at 45 DEG C, being then evacuated to pressure is -0.06MPa,
Lithium battery A1 is obtained after sealing, chemical property is as shown in table 1.
Embodiment 2
(1) anode preparation
1.5kg PVDF is dissolved in 28.5kgNMP, the PVDF glue that mass concentration is 5% is obtained；By 96.5kg carbon
(it is 12 μm, tap density 1g/cm that volume average particle size is distributed D50 to coated LiFePO 4 for lithium ion batteries3, specific surface area 10m2/ g), 1kg leads
Electro-graphitic, 1kg graphene and above-mentioned PVDF glue are stirred evenly under conditions of 40 DEG C of vacuum degree≤- 0.08MPa to be made just
Pole slurry；
By anode sizing agent be coated on a thickness of 18 μm graphitization alkene layer aluminium foil tow sides (graphene layer be 2 μm+thickness
Aluminium foil for 14 μm), then 120 DEG C drying, under the pressure of 1.6MPa after roll-in on cutting machine cutting obtain having a size of
The anode of 5300mm × 74mm × 20 μm, obtaining surface density is 155g/m2, compacted density 2.4g/cm3Anode.
(2) prepared by cathode
2.5kg CMC is dissolved in 165kg deionized water, the CMC glue that mass concentration is 1.5% is obtained；It will
95.9kg artificial graphite (tap density 0.93g/cm3, specific surface area 2.8m2/ g), 0.8kg electrically conductive graphite, 0.8kg carbon nanometer
Pipe is stirred evenly under conditions of 20 DEG C of vacuum degree≤- 0.08MPa with above-mentioned CMC glue negative electrode slurry is made；
By negative electrode slurry be coated on a thickness of 12 μm graphitization alkene layer copper foil tow sides (graphene layer be 2 μm+thickness
Copper foil for 8 μm), then 120 DEG C drying, under the pressure of 1.6MPa after roll-in on cutting machine cutting obtain having a size of
The cathode of 5500mm × 78mm × 13 μm, obtaining surface density is 67g/m2, compacted density 1.7g/m3。
(3) by LiPF6With ethylene sulfite, glycol dimethyl ether, ethylene carbonate (EC), methyl ethyl carbonate (EMC)
LiPF is configured to dimethyl carbonate (DMC)6Solution that concentration is 1.3mol/L (wherein, the weight ratio of EC, EMC and DMC are 1:
1:1), on the basis of the total weight of electrolyte, wherein the content of propylene sulfite is total weight 0.5%, the second two of electrolyte
The content of diethylene glycol dimethyl ether propylene sulfite is the total weight 0.5% of electrolyte.
The cathode that anode, membrane layer polyethylene (PE), (2) that (1) obtains obtain successively is wound into up- coiler stacking
The electrode group of scroll is fitted into the square aluminum hull that length is respectively 148mm, 26mm, 91mm in such a way that 2 battery cores are in parallel,
Again by aluminum hull cover board and aluminum hull laser welding, electrolyte is injected, inert gas is then filled with into lithium battery, until pressure is
3MPa, by lithium battery at 20 DEG C it is upright for 24 hours, then the upright 6h at 55 DEG C, being then evacuated to pressure is -0.05MPa, sealing
After obtain lithium battery A2, chemical property is as shown in table 1.
Embodiment 3
(1) anode preparation
2.5kg PVDF is dissolved in 22.5kg NMP, the PVDF glue that mass concentration is 10% is obtained；By 96.5kg
(it is 8 μm, tap density 01.3g/cm that volume average particle size is distributed D50 to carbon-coated LiFePO 4 for lithium ion batteries3, specific surface area 18m2/g)、
0.5kg electrically conductive graphite, 0.5kg graphene stir evenly under conditions of 40 DEG C of vacuum degree≤- 0.08MPa with above-mentioned PVDF glue
Anode sizing agent is made；
By anode sizing agent be coated on a thickness of 24 μm graphitization alkene layer aluminium foil tow sides (graphene layer be 2 μm+thickness
Aluminium foil for 20 μm), then 120 DEG C drying, under the pressure of 1.6MPa after roll-in on cutting machine cutting obtain having a size of
The anode of 3320mm × 180mm × 20 μm, obtaining surface density is 156g/m2, compacted density 2.2g/cm3Anode.
(2) prepared by cathode
5kg CMC is dissolved in 273kg deionized water, the CMC glue that mass concentration is 1.8% is obtained；By 94.6kg
Artificial graphite (tap density 1.15g/cm3, specific surface area 4.3m2/ g), 0.2kg electrically conductive graphite, 0.2kg carbon nanotube with it is upper
CMC glue is stated to be stirred evenly under conditions of 20 DEG C of vacuum degree≤- 0.08MPa negative electrode slurry is made；
By negative electrode slurry be coated on a thickness of 12 μm graphitization alkene layer copper foil tow sides (graphene layer be 2 μm+thickness
Copper foil for 8 μm), then 120 DEG C drying, under the pressure of 1.6MPa after roll-in on cutting machine cutting obtain having a size of
The cathode of 3400mm × 184mm × 13 μm, obtaining surface density is 80g/m2, compacted density 1.5g/m3。
(3) by LiPF6With ethylene sulfite, glycol dimethyl ether, ethylene carbonate (EC), methyl ethyl carbonate (EMC)
LiPF is configured to dimethyl carbonate (DMC)6Solution that concentration is 1mol/L (wherein, the weight ratio of EC, EMC and DMC are 1:1:
1), on the basis of the total weight of electrolyte, wherein the content of propylene sulfite is the total weight 3% of electrolyte, ethylene glycol two
The content of methyl ether propylene sulfite is the total weight 3% of electrolyte.
The cathode that anode, membrane layer polyethylene (PE), (2) that (1) obtains obtain successively is wound into up- coiler stacking
The electrode group of scroll is fitted into the square aluminum hull that length is respectively 148mm, 53mm, 200mm in such a way that 2 battery cores are in parallel,
Again by aluminum hull cover board and aluminum hull laser welding, electrolyte is injected, inert gas is then filled with into lithium battery, until pressure is
0.3MPa, by lithium battery at 35 DEG C upright 6h, then at 40 DEG C it is upright for 24 hours, be then evacuated to pressure be -0.08MPa, it is close
It is honored as a queen to obtain lithium battery A3, chemical property is as shown in table 1.
Embodiment 4
According to the method for embodiment 1, unlike, it is described anode the preparation method is as follows:
1kg PVDF is dissolved in 12kg NMP, the PVDF glue that mass concentration is 7.5% is obtained；By 97.7kg carbon packet
Covering LiFePO4, (it is 7 μm, tap density 0.8g/cm that volume average particle size, which is distributed D50,3, specific surface area 22m2/ g), 0.5kg second
Acetylene black, 0.8kg graphene and above-mentioned PVDF glue are stirred evenly under conditions of 40 DEG C of vacuum degree≤- 0.08MPa to be made just
Pole slurry；
By anode sizing agent be coated on a thickness of 18 μm graphitization alkene layer aluminium foil tow sides (graphene layer be 1 μm+thickness
Aluminium foil for 16 μm), then 120 DEG C drying, under the pressure of 1.6MPa after roll-in on cutting machine cutting obtain having a size of
The anode of 2350mm × 180mm × 20 μm, obtaining surface density is 150g/m2, compacted density 2g/cm3Anode, obtain lithium electricity
Pond A4, chemical property are as shown in table 1.
Embodiment 5
According to the method for embodiment 1, unlike, it is described anode the preparation method is as follows:
3.5kg PVDF is dissolved in 31.5kg NMP, the PVDF glue that mass concentration is 10% is obtained；By 94kg carbon
(it is 15 μm, tap density 1.5g/cm that volume average particle size is distributed D50 to coated LiFePO 4 for lithium ion batteries3, specific surface area 22m2/g)、1kg
Electrically conductive graphite, 1.5kg graphene and above-mentioned PVDF glue are stirred evenly under conditions of 40 DEG C of vacuum degree≤- 0.08MPa to make
Obtain anode sizing agent；
By anode sizing agent be coated on a thickness of 20 μm graphitization alkene layer copper foil tow sides (graphene layer be 3 μm+thickness
Aluminium foil for 14 μm), then 120 DEG C drying, under the pressure of 1.6MPa after roll-in on cutting machine cutting obtain having a size of
The anode of 2350mm × 180mm × 20 μm, obtaining surface density is 168g/m2, compacted density 2.6g/cm3Anode, obtain lithium
Battery A5, chemical property are as shown in table 1.
Embodiment 6
According to the method for embodiment 1, unlike, the cathode the preparation method is as follows:
2.5kg CMC is dissolved in 156kg deionized water, the CMC glue that mass concentration is 1.6% is obtained；By 97kg
Artificial graphite (tap density 0.8g/cm3, specific surface area 5m2/ g), 0.2kg electrically conductive graphite, 0.3kg carbon nanotube with it is above-mentioned
CMC glue is stirred evenly under conditions of 20 DEG C of vacuum degree≤- 0.08MPa negative electrode slurry is made；
By negative electrode slurry be coated on a thickness of 11 μm graphitization alkene layer copper foil tow sides (graphene layer be 2 μm+thickness
Copper foil for 7 μm), then 120 DEG C drying, under the pressure of 1.6MPa after roll-in on cutting machine cutting obtain having a size of
The cathode of 2480mm × 184mm × 13 μm, obtaining surface density is 82g/m2, compacted density 1.86g/m3, lithium battery A6 is obtained,
Its chemical property is as shown in table 1.
Embodiment 7
According to the method for embodiment 1, unlike, the cathode the preparation method is as follows:
5kg CMC is dissolved in 273kg deionized water, the CMC glue that mass concentration is 1.8% is obtained；By 94kg people
Make graphite (tap density 1.2g/cm3, specific surface area 2m2/ g), 0.5kg electrically conductive graphite, 0.5kg carbon nanotube and above-mentioned CMC
Glue is stirred evenly under conditions of 20 DEG C of vacuum degree≤- 0.08MPa negative electrode slurry is made；
By negative electrode slurry be coated on a thickness of 13 μm graphitization alkene layer copper foil tow sides (graphene layer be 1 μm+thickness
Copper foil for 11 μm), then 120 DEG C drying, under the pressure of 1.6MPa after roll-in on cutting machine cutting obtain having a size of
The cathode of 2480mm × 184mm × 13 μm, obtaining surface density is 63g/m2, compacted density 1.35g/m3, lithium battery A7 is obtained,
Its chemical property is as shown in table 1.
Embodiment 8
According to the method for embodiment 1, unlike, the configuration method of the electrolysis is as follows: by LiPF6With sulfurous acid propylene
Ester, glycol dimethyl ether, ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) are configured to LiPF6It is dense
The solution (wherein, the weight ratio of EC, EMC and DMC are 1:0.8:0.8) that degree is 1.3mol/L, using the total weight of electrolyte as base
Standard, wherein the content of propylene sulfite is total weight 1.5%, the content of glycol dimethyl ether propylene sulfite of electrolyte
For the total weight 2% of electrolyte, lithium battery A8 is obtained, chemical property is as shown in table 1.
Embodiment 9
According to the method for embodiment 1, unlike, the configuration method of the electrolysis is as follows: (3) are by LiPF6With carbonic acid Asia
Vinyl acetate, propylene sulfite, glycol dimethyl ether, ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate
(DMC) it is configured to LiPF6The solution (wherein, the weight ratio of EC, EMC and DMC are 1:1.2:1.2) that concentration is 1.3mol/L, with
On the basis of the total weight of electrolyte, wherein the content of vinylene carbonate is the total weight 1% of electrolyte, vinylene carbonate
Content is the total weight 1% of electrolyte, the total weight 2% that the content of glycol dimethyl ether propylene sulfite is electrolyte, is obtained
To lithium battery A9, chemical property is as shown in table 1.
Comparative example 1
According to the method for embodiment 1, unlike, the plus plate current-collecting body is the aluminium foil with a thickness of 16 μm, obtains lithium electricity
Pond B1, chemical property are as shown in table 1.
Comparative example 2
According to the method for embodiment 1, unlike, the negative current collector is the copper foil with a thickness of 9 μm, obtains lithium battery
B2, chemical property are as shown in table 1.
Comparative example 3
According to the method for embodiment 1, unlike, propylene sulfite is not contained in the electrolyte, obtains lithium battery
B3, chemical property are as shown in table 1.
Comparative example 4
According to the method for embodiment 1, unlike, glycol dimethyl ether sulfurous acid propylene is not contained in the electrolyte
Ester, obtains lithium battery B4, and chemical property is as shown in table 1.
Comparative example 5
According to the method for embodiment 1, it unlike, in the impregnation process of electrolyte, is not injected to lithium battery interior lazy
Property gas, obtains lithium battery B5, chemical property is as shown in table 1.
Test method:
1, each lithium battery in Examples 1 to 9 and comparative example 1~4 is filled at 25 DEG C, in a manner of constant-current constant-voltage charging
Electricity, limitation electric current are 0.05C, voltage range 2.8-3.55V, recycle 10000 times, calculate separately the 1st discharge capacity C, energy
Capacity retention ratio R after imitating ratio and circulation 10000 times.
2, each lithium battery in Examples 1 to 9 and comparative example 1~4 is filled at -20 DEG C, in a manner of constant-current constant-voltage charging
Electricity, limitation electric current are 0.05C, voltage range 2.0-3.55V, calculate initial discharge capacity ratio (%) C1.
3, it charges, limits to each lithium battery in Examples 1 to 9 and comparative example 1~4 at 55 DEG C, with constant voltage charging method
Electric current processed is 0.5C, voltage range 2.8-3.55V, is recycled 10000 times, and initial discharge capacity ratio (%) C2 is calculated.
Inner walkway method: after single battery charging is full, with accuracy ± 0.1%, voltage and electric current are not less than 0.5 grade,
Frequency is that the AC internal Resistance tester of 1.0kHz ± 0.1kHz directly measures.
The calculation method of Energy Efficiency Ratio: the same discharge energy (Wh) circulated within the scope of assigned voltage of battery and regulation electricity
Press the ratio of the rechargeable energy (Wh) in range.
The capacity retention ratio of lithium battery is tested and calculated according to GR/T 31484-2015.
The initial discharge capacity of lithium battery is tested and calculated according to GR/T 31484-2015.
Table 1: the performance table of each lithium battery in Examples 1 to 9 and comparative example 1~4
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.It is further to note that described in above-mentioned specific embodiment
Each particular technique feature can be combined in any appropriate way in the case of no contradiction, in order to avoid not
Necessary repetition, the invention will not be further described in various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (6)
1. a kind of preparation method of lithium battery, which is characterized in that the lithium battery includes anode, cathode, diaphragm and electrolyte, institute
Stating anode includes plus plate current-collecting body and coated in the positive electrode on the plus plate current-collecting body, wherein the plus plate current-collecting body is
Graphitization alkene layer aluminium foil, the graphitization alkene layer aluminium foil include aluminium foil and the first graphite ene coatings coated in aluminium foil surface,
Middle aluminium foil with a thickness of 14-20 μm；The first graphite ene coatings with a thickness of 1-3 μm；The cathode includes negative current collector
With the negative electrode material being coated on the negative current collector, wherein the negative current collector is graphitization alkene layer copper foil, the painting
Graphene layer copper foil includes copper foil and the second graphite ene coatings coated in copper foil surface, the copper foil with a thickness of 7-11 μm；
The second graphite ene coatings with a thickness of 1-3 μm；
The positive electrode includes positive electrode active materials, conductive agent, binder, and the positive electrode active materials include carbon coating phosphoric acid
The volume average particle size distribution D50 of iron lithium, the carbon-coated LiFePO 4 for lithium ion batteries is 7 ~ 15 μm, 0.8 ~ 1.5g/cm of tap density3, ratio
Surface area is 7 ~ 22 m2/g；
The negative electrode material includes negative electrode active material, conductive agent and binder；The negative electrode active material includes artificial graphite,
The tap density of the artificial graphite is 0.8 ~ 1.2g/cm3, 2 ~ 5 m of specific surface area2/g；
It the described method comprises the following steps:
(1) positive preparation；
(2) preparation of cathode；
(3) electrolyte will be injected after the positive electrode, the negative electrode and the separator coiling and molding, inert gas is then filled with into lithium battery, until pressure
By force be 0.3 ~ 3MPa, then by lithium battery at 20 ~ 35 DEG C upright 6-24h, then the upright 6-24h at 40-55 DEG C, then take out true
Sky to pressure is to obtain lithium battery after sealing under -0.08 ~ -0.05MPa.
2. according to the method described in claim 1, wherein, the electrolyte includes ethylene carbonate, methyl ethyl carbonate and carbonic acid
Dimethyl ester, and the volume ratio of the ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate is 1:(0.8 ~ 1.2): (0.8 ~
1.2).
3. according to the method described in claim 2, wherein, coalescing agent and/or glycol dinitrate are also contained in the electrolyte
Ether；
The coalescing agent is selected from least one of vinylene carbonate, propylene sulfite and ethylene sulfite.
4. according to the method described in claim 3, wherein, on the basis of the total weight of the electrolyte, the coalescing agent
Content is 0.5 ~ 3 weight %；And/or
The content of the glycol dimethyl ether is 0.5 ~ 3 weight %.
5. according to the method described in claim 1, wherein, on the basis of the total weight of positive electrode, the positive electrode active materials
Content be 94-97.7 weight %, the content of conductive agent is 0.8 ~ 3 weight %, the content of binder be 1.0 ~ 3.5 weight %；With/
Or
The conductive agent in acetylene black, conductive black, graphene and carbon nanotube at least two；And/or
The binder is polyvinylidene fluoride.
6. according to the method described in claim 1, wherein, on the basis of the total weight of lithium cell cathode material, the cathode is living
Property material content be 94-97 weight %, the content of conductive agent is 0.4 ~ 1.6 weight %, the content of binder be 2.5 ~ 5 weight %；
And/or
The conductive agent in carbon nanotube, acetylene black, conductive black, graphite agent KS at least two；And/or
The binder is carboxymethyl cellulose.
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| CN110247013B (en) * | 2018-03-08 | 2022-06-03 | 宁德时代新能源科技股份有限公司 | Positive pole piece and electrochemical device containing same |
| CN108428867B (en) * | 2018-03-09 | 2019-08-16 | 深圳市溢骏科技有限公司 | Fast charging type lithium ion battery and preparation method thereof |
| CN109148988A (en) * | 2018-08-28 | 2019-01-04 | 孙战 | A kind of lithium-ion battery electrolytes rapid osmotic method |
| CN110265627B (en) * | 2018-09-28 | 2020-09-29 | 宁德时代新能源科技股份有限公司 | Positive electrode plate and lithium ion secondary battery |
| CN109509909B (en) * | 2018-10-17 | 2020-07-03 | 宁德时代新能源科技股份有限公司 | Secondary battery |
| CN111403799B (en) * | 2020-03-09 | 2022-03-18 | 广西华政新能源科技有限公司 | Special-shaped lithium battery and vehicle-mounted kettle |
| CN112952030A (en) * | 2020-03-27 | 2021-06-11 | 宁德新能源科技有限公司 | Positive pole piece, electrochemical device comprising positive pole piece and electronic device |
| CN114188507A (en) * | 2021-10-29 | 2022-03-15 | 中国石油大学(北京) | Negative pole piece, preparation method thereof and lithium ion battery |
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