CN108417921A - A kind of preparation method and battery of high energy density cells - Google Patents
A kind of preparation method and battery of high energy density cells Download PDFInfo
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- CN108417921A CN108417921A CN201810132918.XA CN201810132918A CN108417921A CN 108417921 A CN108417921 A CN 108417921A CN 201810132918 A CN201810132918 A CN 201810132918A CN 108417921 A CN108417921 A CN 108417921A
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a kind of preparation methods of high energy density cells, include the following steps：S1. processing is packaged to positive and negative anodes pole piece using aluminum plastic film and obtains packaging electric core；S2. fluid injection sealing is carried out to the battery core；S3. first time evacuation is carried out to product after fluid injection；S4. preliminary filling processing is carried out to obtained product；S5. second of evacuation is carried out to product；S6. finished battery is obtained after chemical conversion, partial volume.Battery prepared by the present invention, energy density reach 250Wh/kg or more, while having excellent multiplying power and cycle performance.
Description
Technical field
The present invention relates to field of batteries more particularly to the preparation methods and battery of a kind of high energy density cells.
Background technology
Lithium ion battery is a kind of high performance secondary cell, volume and weight energy density height high with operating voltage,
Long lifespan, self-discharge rate be low, memory-less effect and it is environmentally friendly the advantages that, be widely used in mobile communication equipment, notebook
Computer takes the photograph the fields such as videocorder, PDA (personal digital assistant), digital camera, electric tool and torpedo, guided missile.
Because soft bag lithium ionic cell is frivolous, appearance and size is flexible, can more meet integrated design requirement, in high-end intelligent hand
The machine field market share steps up.Introducing soft bag lithium ionic cell by internal battery design, (being different from conventional mobile phone can replace
The aluminum hull packaging for changing battery, mainly uses laminated aluminum film), traditional aluminum-shell battery is compared, is segmented market in consumption electronic product
It plays a key effect.
The mass energy density of soft bag lithium ionic cell is higher than aluminum-shell battery, and the battery (2Ah~5Ah) of same volume is soft
Packet lithium ion battery 10%-20% lighter than aluminum-shell battery or so.On the one hand, middle and high end electronic consumer products are (such as intelligent hand
Machine, tablet computer, iPad etc.) increasingly frivolous, integrated portability, and then the demand to battery energy density and product appearance carries
It rises, soft bag lithium ionic cell has the potential of replacement aluminum-shell battery under conditions of technical maturity gradually promotes, and advantage will be into
One step highlights.
With the explosive growth of lithium ion battery, to the course continuation mileage etc. of electric vehicle, there has also been higher and higher in market
Requirement, therefore the requirement to power battery energy density is also higher and higher.CN102024943A and CN101859888A patents
In, the higher rich lithium material of gram volume is proposed, although the gram volume of rich lithium material can reach 200mAh/g or more, due to itself
Lattice structure is unstable, there are first charge discharge efficiency low and high temperature storage difference and cyclic process in phase transformation the problems such as, it is difficult in power battery
On obtain large-scale application.In terms of negative material, more and more producers are attempting silicon-carbon cathode material, but since silicon materials exist
Bulk effect in charge and discharge process, cell expansion, dusting are extremely serious, main at present still applied in cylindrical battery.
In conclusion there is also many defects for the power battery of the prior art, the demand of practical application is cannot be satisfied, because
This, it is necessary to the prior art is improved.
Invention content
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of preparation method of high energy density cells and electricity
Pond.
The present invention is achieved by the following technical solutions：
A kind of preparation method of high energy density cells, includes the following steps：
S1. processing is packaged to positive and negative anodes pole piece using aluminum plastic film and obtains packaging electric core；
S2. fluid injection sealing is carried out to the battery core；
S3. first time evacuation is carried out to product after fluid injection；Evacuating parameter is：Vacuum degree -80~-101KPa, vacuum
Be delayed 0.1-5S, packaging time 1-10S, air pressure 0.1-0.8MPa, upper 160-200 DEG C of low head temperature；
S4. preliminary filling processing is carried out to obtained product；
S5. second of evacuation is carried out to product；Evacuating parameter is：Vacuum degree -80~-101KPa, vacuum delay
0.1-5S, packaging time 1-10S, air pressure 0.1-0.8MPa, upper 160-200 DEG C of low head temperature；
S6. finished battery is obtained after chemical conversion, partial volume.
It evacuates for the first time primarily to by discharges such as the micro moisture and air that are introduced in injection process；Second of pumping
Sky is discharged in order to which preliminary filling to be formed to the gas generated in SEI membrane process, so that it is guaranteed that not having gas in battery, reduces gas pair
The influence of battery performance.
Preferably, further include between the step S1 and step S2：Baking processing is carried out to battery core.
Preferably, further comprising the steps of before the step S1：
S01. the preparation of anode sizing agent, negative electrode slurry；
S02. the coating of anode, cathode；It is coated with anode sizing agent on plus plate current-collecting body and obtains positive plate, in negative current collector
Upper coating negative electrode slurry obtains negative plate；
S03. the roll-in and film-making of positive plate, negative plate；
S04. the baking of positive plate, negative plate；
S05. lamination prepares battery core；
S06. the welding of positive pole ear, negative lug.
Preferably, the step S01 is specifically included：By positive active material, positive conductive agent and positive electrode binder into
Row is sieved after being mixed up to the anode sizing agent；The mass percent of wherein each substance is as follows：Positive active material 90-
98%, positive conductive agent 0.5-5%, positive electrode binder 1.5-5%.
Preferably, after negative electrode active material, cathode conductive agent, cathode thickener, negative electrode binder being mixed
It is sieved up to the negative electrode slurry；The mass percent of wherein each substance is as follows：Negative electrode active material 90-96%, negative conductive
Agent 1-3%, cathode thickener 1-3%, negative electrode binder 2-4%.
Preferably, the viscosity of the anode sizing agent is 3000-8000mPas, and the viscosity of the negative electrode slurry is 2000-
6000mPa·s。
Preferably, the positive active material is multicomponent material of the nickel content higher than 60% by cladding processing, cladding
Agent is one or more in aluminium oxide, magnesia, zirconium oxide.
Preferably, the positive conductive agent is graphene slurry, carbon nano tube paste, one kind in carbon nano-fiber or more
Kind.
Preferably, the positive electrode binder is Kynoar or polytetrafluoroethylene (PTFE).
Preferably, the negative electrode active material is the mixture of natural graphite or natural graphite and artificial graphite.
Preferably, the cathode thickener is sodium carboxymethylcellulose, and the negative electrode binder is butadiene-styrene rubber, polypropylene
Acid resin or polyimides.
Preferably, the cathode conductive agent is conductive black, superconduction carbon, electrically conductive graphite, crystalline flake graphite, carbon nanotube or carbon
Nanofiber.
Preferably, the plus plate current-collecting body is aluminium foil, and thickness is 12-15 μm；The negative current collector is copper foil, and thickness is
6-10μm。
Preferably, the diaphragm of the battery is boehmite coated separator, wherein basement membrane is PP or PE, the diaphragm total thickness
Degree is 12-20 μm.
Preferably, electrolyte is LiPF6 in the electrolyte that the fluid injection uses, in solvent EC, DEC, PC, DMC, EMC
At least two mixture.
Preferably, the surface density of the positive plate is 30-40mg/cm2, compacted density 3.0-3.6g/cc；The cathode
The surface density of piece is 15-20mg/cm2, compacted density 1.4-1.7g/cc.
Preferably, the baking temperature of the positive and negative anodes pole piece is 80~130 DEG C, and vacuum degree is -0.085~-0.095MPa,
Baking time is 12~24 hours, is continuously vacuumized in baking process.
Preferably, the battery core baking temperature is 50~85 DEG C, and vacuum degree is -0.085~-0.095MPa, baking time
It is 12~48 hours, is continuously vacuumized in baking process.
Preferably, preliminary filling processing is all made of ladder charging work step with chemical conversion, and electric current incrementally increases, and ensures to be formed
SEI films are uniform and fine and close.
A kind of high energy density cells, adopt and are prepared with the aforedescribed process.
Preferably, the anode sizing agent is grouped as by the group of following mass percent：Positive active material 90-98%, just
Pole conductive agent 0.5-5%, positive electrode binder 1.5-5%；The negative electrode slurry is grouped as by the group of following mass percent：Cathode
Active material 90-96%, cathode conductive agent 1-3%, cathode thickener 1-3%, negative electrode binder 2-4%.
Preferably, the positive active material is multicomponent material of the nickel content higher than 60% by cladding processing, cladding
Agent is one or more in aluminium oxide, magnesia, zirconium oxide.
Preferably, the negative electrode active material is the mixture of natural graphite or natural graphite and artificial graphite.
The beneficial effects of the invention are as follows：
(1) preparation method of high energy density cells of the invention carries out first time evacuation after fluid injection, can incite somebody to action
The discharges such as the micro moisture and air that are introduced in injection process avoid causing harmful effect to the performance of battery；
(2) preparation method of high energy density cells of the invention has carried out second of evacuation behaviour after preliminary filling is completed
Make, preliminary filling is formed to the gas generated in SEI membrane process and is discharged, so that it is guaranteed that there is no gas in battery, reduces gas to battery
The influence of performance；
(3) preparation method of high energy density cells of the invention, preliminary filling processing are all made of ladder charging work step with chemical conversion,
Electric current incrementally increases, to ensure that the SEI films to be formed are uniform and fine and close；
(4) battery prepared by the present invention, energy density reaches 250Wh/kg or more, while having excellent multiplying power and cycle
Performance.
Description of the drawings
It, below will be to required in embodiment or description of the prior art in order to illustrate more clearly of technical scheme of the present invention
The attached drawing used is briefly described, it should be apparent that, the accompanying drawings in the following description is only the embodiment of the present invention, for this
For the those of ordinary skill of field, without creative efforts, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 is discharge performance curve of the battery under 1c, 2c, 3c, 4c, 5c multiplying power；
Fig. 2 is the capacity retention ratio curve of battery.
Specific implementation mode
Below in conjunction with the attached drawing in the present invention, technical solution in the embodiment of the present invention is clearly and completely retouched
It states, it is clear that described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on this hair
Embodiment in bright, the every other reality that those of ordinary skill in the art are obtained under the premise of not making creative work
Example is applied, shall fall within the protection scope of the present invention.
Embodiment 1
The invention discloses a kind of preparation methods of high energy density cells, include the following steps：
S01. the preparation of anode sizing agent, negative electrode slurry；
Positive electrode binder Kynoar is dissolved in N-Methyl pyrrolidone organic solvent, 2-4h, prepare glue are stirred；
Positive conductive agent carbon nano-fiber is added in glue again and is stirred 1 hour, positive active material NCM622 is added immediately, continues height
Speed stirring 2-4h, viscosity reach 3000-8000mPas, complete sieving after stirring and obtain required anode sizing agent；Wherein each substance
Mass percent it is as follows：Positive active material 90%, positive conductive agent 5%, positive electrode binder 5%；
Glue is stirred to get by cathode thickener sodium carboxymethylcellulose is soluble in water, cathode conductive agent carbon black is added and stirs
It mixes 1 hour, negative electrode active material natural graphite is added immediately and stirs 2-4h, negative electrode binder polyacrylic resin is added and adjusts slurry
Material viscosity reaches 2000~6000mPas, is sieved up to required negative electrode slurry；The mass percent of wherein each substance is as follows：It is negative
Pole active material 90%, cathode conductive agent 3%, cathode thickener 3%, negative electrode binder 4%.
S02. the coating of anode, cathode；It is coated with anode sizing agent on plus plate current-collecting body and obtains positive plate, in negative current collector
Upper coating negative electrode slurry obtains negative plate；The plus plate current-collecting body is aluminium foil, and thickness is 12 μm；The negative current collector is copper
Foil, thickness are 6 μm.
S03. the roll-in and film-making of positive plate, negative plate；The positive plate, negative plate are rolled, finally cut, is rushed
Piece obtains the positive and negative plate of required size；The surface density of the positive plate is 30mg/cm2, compacted density 3.0g/cc；It is described
The surface density of negative plate is 15mg/cm2, compacted density 1.4g/cc.
S04. the baking of positive plate, negative plate；The positive and negative plate cut is placed under vacuum state and is toasted；Institute
The baking temperature for stating positive and negative anodes pole piece is 80 DEG C, and vacuum degree is -0.085~-0.095MPa, and baking time is 24 hours, is being dried
It is continuously vacuumized during roasting.
S05. lamination prepares battery core；By after baking positive and negative plate and boehmite coated separator (basement membrane PP) pass through it is folded
Piece machine completes assembling and forms battery core；The diaphragm overall thickness is 12 μm.
S06. the welding of positive pole ear, negative lug；Positive pole ear, negative lug are respectively welded pre- in positive and negative anodes pole piece
It stays on collector；
S1. the encapsulation of aluminum plastic film, battery core is fitted into aluminum plastic film and is packaged；
Battery core after encapsulation is subjected to baking processing；The battery core baking temperature be 50 DEG C, vacuum degree be -0.085~-
0.095MPa, baking time are 48 hours, are continuously vacuumized in baking process.
S2. fluid injection sealing is carried out to the battery core；For LiPF6, solvent is electrolyte in the electrolyte that the fluid injection uses
The mixture of EC, DEC.
S3. first time evacuation is carried out to product after fluid injection；Evacuating parameter is：Vacuum degree -91KPa, vacuum delay 2S,
Packaging time 5S, air pressure 0.5MPa, 180 DEG C of upper low head temperature；
S4. preliminary filling processing is carried out to obtained product；
S5. second of evacuation is carried out to product；Evacuating parameter is：Vacuum degree -95KPa, vacuum are delayed 3S, when encapsulation
Between 6S, air pressure 0.6MPa, 185 DEG C of upper low head temperature；
S6. finished battery is obtained after chemical conversion, partial volume.
It evacuates for the first time primarily to by discharges such as the micro moisture and air that are introduced in injection process；Second of pumping
Sky is discharged in order to which preliminary filling to be formed to the gas generated in SEI membrane process, so that it is guaranteed that not having gas in battery, reduces gas pair
The influence of battery performance.
The preliminary filling processing is all made of ladder charging work step with chemical conversion, and electric current incrementally increases, to ensure the SEI films to be formed
It is uniform and fine and close.
Wherein preliminary filling work step is as shown in the table：
| Work step serial number | Work step state | Electric current/mA | Blanking voltage/mV | Time/min |
| 1 | It stands | / | / | 2 |
| 2 | Constant current charge | 0.05C | 3370 | 100 |
| 3 | Constant current charge | 0.1C | 3370 | 60 |
| 4 | Constant current charge | 0.2C | 3600 | / |
| 5 | It stands | / | / | 5 |
| 6 | Terminate | / | / | / |
It is as shown in the table to be melted into work step：
| Work step serial number | Work step state | Electric current/mA | Blanking voltage/mV | Time/min |
| 1 | It stands | / | / | 2 |
| 2 | Constant current charge | 0.2C | 3900 | 300 |
| 3 | Constant current charge | 0.45C | 4200 | / |
| 4 | It stands | / | / | 5 |
| 5 | Terminate | / | / | / |
Electric performance test, energy density 251Wh/kg are carried out to the finished battery below.Fig. 1 be battery 1c,
Discharge performance curve under 2c, 3c, 4c, 5c multiplying power, abscissa are capacity (Ah), and ordinate is voltage (V)；Fig. 2 is battery
Capacity retention ratio curve, it is seen then that after 525 cycles, capacity retention ratio is still up to 95.8%.
Following table is capacity retention ratio of the battery under different multiplying：
| Multiplying power | 1C | 2C/1C | 3C/1C | 4C/1C | 5C/1C |
| Capacity retention ratio | 100% | 99.35% | 99.17% | 97.95% | 94.2% |
Comparative example 1
Present embodiment discloses a kind of preparation methods of battery, include the following steps：S1. use aluminum plastic film to positive and negative anodes pole
Piece is packaged processing and obtains packaging electric core；S2. fluid injection sealing is carried out to the battery core；S3. chemical conversion, obtain after partial volume battery at
Product.Raw material and experiment parameter are same as Example 1 used in this method, the difference is that only that the present embodiment does not carry out
Secondary evacuation and preliminary filling processing.It uses this method to prepare the energy density of battery as 240Wh/kg, is recycled by 500 times
Later, capacity retention ratio 85%.
Comparative example 2
Present embodiment discloses a kind of preparation methods of battery, and present embodiment discloses a kind of preparation method of battery, packets
Include following steps：S1. processing is packaged to positive and negative anodes pole piece using aluminum plastic film and obtains packaging electric core；S2. to the battery core into
Row fluid injection is sealed；S3. first time evacuation is carried out to product after fluid injection；S4. finished battery is obtained after chemical conversion, partial volume.The party
Raw material and experiment parameter are same as Example 1 used in method, the difference is that only that the present embodiment does not carry out at preliminary filling
Reason and second of evacuation.It uses this method to prepare the energy density of battery as 242Wh/kg, it is recycled by 500 times
Afterwards, capacity retention ratio 92%.
Embodiment 2
The invention discloses a kind of preparation methods of high energy density cells, include the following steps：
S01. the preparation of anode sizing agent, negative electrode slurry；
Positive electrode binder polytetrafluoroethylene (PTFE) is dissolved in N-Methyl pyrrolidone organic solvent, 2-4h, prepare glue are stirred；
Positive conductive agent carbon nano tube paste is added in glue again and is stirred 1 hour, positive active material NCA ternary materials are added immediately
Material continues high-speed stirred 2-4h, and viscosity reaches 3000-8000mPas, completes sieving after stirring and obtains required anode sizing agent；Its
In each substance mass percent it is as follows：Positive active material 98%, positive conductive agent 0.5%, positive electrode binder 1.5%；
Glue is stirred to get by cathode thickener sodium carboxymethylcellulose is soluble in water, adds cathode conductive agent superconduction carbon
Stirring 1 hour, the mixture that negative electrode active material natural graphite and artificial graphite are added immediately stir 2-4h, and cathode is added and bonds
Agent butadiene-styrene rubber adjusts slurry viscosity and reaches 2000~6000mPas, is sieved up to required negative electrode slurry；Wherein each substance
Mass percent is as follows：Negative electrode active material 96%, cathode conductive agent 1%, cathode thickener 1%, negative electrode binder 2%.
S02. the coating of anode, cathode；It is coated with anode sizing agent on plus plate current-collecting body and obtains positive plate, in negative current collector
Upper coating negative electrode slurry obtains negative plate；The plus plate current-collecting body is aluminium foil, and thickness is 15 μm；The negative current collector is copper
Foil, thickness are 10 μm.
S03. the roll-in and film-making of positive plate, negative plate；The positive plate, negative plate are rolled, finally cut, is rushed
Piece obtains the positive and negative plate of required size；The surface density of the positive plate is 40mg/cm2, compacted density 3.6g/cc；It is described
The surface density of negative plate is 20mg/cm2, compacted density 1.7g/cc.
S04. the baking of positive plate, negative plate；The positive and negative plate cut is placed under vacuum state and is toasted；Institute
The baking temperature for stating positive and negative anodes pole piece is 130 DEG C, and vacuum degree is -0.085~-0.095MPa, and baking time is 12 hours, is being dried
It is continuously vacuumized during roasting.
S05. lamination prepares battery core；By after baking positive and negative plate and boehmite coated separator (basement membrane PE) pass through it is folded
Piece machine completes assembling and forms battery core；The diaphragm overall thickness is 18 μm.
S06. the welding of positive pole ear, negative lug；Positive pole ear, negative lug are respectively welded pre- in positive and negative anodes pole piece
It stays on collector；
S1. the encapsulation of aluminum plastic film, battery core is fitted into aluminum plastic film and is packaged；
Battery core after encapsulation is subjected to baking processing；The battery core baking temperature be 85 DEG C, vacuum degree be -0.085~-
0.095MPa, baking time are 12 hours, are continuously vacuumized in baking process.
S2. fluid injection sealing is carried out to the battery core；For LiPF6, solvent is electrolyte in the electrolyte that the fluid injection uses
The mixture of DMC, EMC.
S3. first time evacuation is carried out to product after fluid injection；Evacuating parameter is：Vacuum degree -80KPa, vacuum delay
0.1S, packaging time 1S, air pressure 0.1MPa, 160 DEG C of upper low head temperature；
S4. preliminary filling processing is carried out to obtained product；
S5. second of evacuation is carried out to product；Evacuating parameter is：Vacuum degree -80KPa, vacuum delay 0.1S, encapsulation
Time 1S, air pressure 0.1MPa, upper low head temperature are 160 DEG C；
S6. finished battery is obtained after chemical conversion, partial volume.
It evacuates for the first time primarily to by discharges such as the micro moisture and air that are introduced in injection process；Second of pumping
Sky is discharged in order to which preliminary filling to be formed to the gas generated in SEI membrane process, so that it is guaranteed that not having gas in battery, reduces gas pair
The influence of battery performance.
The preliminary filling processing is all made of ladder charging work step with chemical conversion, and electric current incrementally increases, to ensure the SEI films to be formed
It is uniform and fine and close.
Wherein preliminary filling work step is as shown in the table：
| Work step serial number | Work step state | Electric current/mA | Blanking voltage/mV | Time/min |
| 1 | It stands | / | / | 2 |
| 2 | Constant current charge | 0.05C | 3370 | 100 |
| 3 | Constant current charge | 0.1C | 3370 | 60 |
| 4 | Constant current charge | 0.2C | 3600 | / |
| 5 | It stands | / | / | 5 |
| 6 | Terminate | / | / | / |
It is as shown in the table to be melted into work step：
| Work step serial number | Work step state | Electric current/mA | Blanking voltage/mV | Time/min |
| 1 | It stands | / | / | 2 |
| 2 | Constant current charge | 0.2C | 3900 | 300 |
| 3 | Constant current charge | 0.45C | 4200 | / |
| 4 | It stands | / | / | 5 |
| 5 | Terminate | / | / | / |
To the finished battery carry out electric performance test, energy density 260Wh/kg, by 500 times recycle after,
Capacity retention ratio is still up to 93%.
Embodiment 3
The invention discloses a kind of preparation methods of high energy density cells, include the following steps：
S01. the preparation of anode sizing agent, negative electrode slurry；
Positive electrode binder Kynoar is dissolved in N-Methyl pyrrolidone organic solvent, 2-4h, prepare glue are stirred；
Positive conductive agent graphene slurry is added in glue again and is stirred 1 hour, positive active material nickel content is added immediately and is higher than
60% NM binary materials continue high-speed stirred 2-4h, and viscosity reaches 3000-8000mPas, and completing to be sieved after stirring obtains
Required anode sizing agent；The mass percent of wherein each substance is as follows：It is positive active material 93%, positive conductive agent 4%, just very viscous
Tie agent 3%；
Glue is stirred to get by cathode thickener sodium carboxymethylcellulose is soluble in water, adds cathode conductive agent scale stone
Ink stirring 1 hour is added negative electrode active material natural graphite and stirs 2-4h, negative electrode binder polyimides is added and adjusts slurry immediately
Material viscosity reaches 2000~6000mPas, is sieved up to required negative electrode slurry；The mass percent of wherein each substance is as follows：It is negative
Pole active material 92%, cathode conductive agent 2%, cathode thickener 2%, negative electrode binder 4%.
S02. the coating of anode, cathode；It is coated with anode sizing agent on plus plate current-collecting body and obtains positive plate, in negative current collector
Upper coating negative electrode slurry obtains negative plate；The plus plate current-collecting body is aluminium foil, and thickness is 13 μm；The negative current collector is copper
Foil, thickness are 8 μm.
S03. the roll-in and film-making of positive plate, negative plate；The positive plate, negative plate are rolled, finally cut, is rushed
Piece obtains the positive and negative plate of required size；The surface density of the positive plate is 35mg/cm2, compacted density 3.5g/cc；It is described
The surface density of negative plate is 18mg/cm2, compacted density 1.5g/cc.
S04. the baking of positive plate, negative plate；The positive and negative plate cut is placed under vacuum state and is toasted；Institute
The baking temperature for stating positive and negative anodes pole piece is 100 DEG C, and vacuum degree is -0.085~-0.095MPa, and baking time is 18 hours, is being dried
It is continuously vacuumized during roasting.
S05. lamination prepares battery core；By after baking positive and negative plate and boehmite coated separator (basement membrane pp) pass through it is folded
Piece machine completes assembling and forms battery core；The diaphragm overall thickness is 16 μm.
S06. the welding of positive pole ear, negative lug；Positive pole ear, negative lug are respectively welded pre- in positive and negative anodes pole piece
It stays on collector；
S1. the encapsulation of aluminum plastic film, battery core is fitted into aluminum plastic film and is packaged；
Battery core after encapsulation is subjected to baking processing；The battery core baking temperature be 65 DEG C, vacuum degree be -0.085~-
0.095MPa, baking time are 31 hours, are continuously vacuumized in baking process.
S2. fluid injection sealing is carried out to the battery core；For LiPF6, solvent is electrolyte in the electrolyte that the fluid injection uses
The mixture of EC, DMC, EMC.
S3. first time evacuation is carried out to product after fluid injection；Evacuating parameter is：Vacuum degree -101KPa, vacuum delay
5S, packaging time 10S, air pressure 0.8MPa, 200 DEG C of upper low head temperature；
S4. preliminary filling processing is carried out to obtained product；
S5. second of evacuation is carried out to product；Vacuum degree -101KPa, vacuum be delayed 5S, packaging time 8S, air pressure
0.8MPa, 200 DEG C of upper low head temperature；
S6. finished battery is obtained after chemical conversion, partial volume.
It evacuates for the first time primarily to by discharges such as the micro moisture and air that are introduced in injection process；Second of pumping
Sky is discharged in order to which preliminary filling to be formed to the gas generated in SEI membrane process, so that it is guaranteed that not having gas in battery, reduces gas pair
The influence of battery performance.
The preliminary filling processing is all made of ladder charging work step with chemical conversion, and electric current incrementally increases, to ensure the SEI films to be formed
It is uniform and fine and close.
Wherein preliminary filling work step is as shown in the table：
| Work step serial number | Work step state | Electric current/mA | Blanking voltage/mV | Time/min |
| 1 | It stands | / | / | 2 |
| 2 | Constant current charge | 0.05C | 3370 | 100 |
| 3 | Constant current charge | 0.1C | 3370 | 60 |
| 4 | Constant current charge | 0.2C | 3600 | / |
| 5 | It stands | / | / | 5 |
| 6 | Terminate | / | / | / |
It is as shown in the table to be melted into work step：
| Work step serial number | Work step state | Electric current/mA | Blanking voltage/mV | Time/min |
| 1 | It stands | / | / | 2 |
| 2 | Constant current charge | 0.2C | 3900 | 300 |
| 3 | Constant current charge | 0.45C | 4200 | / |
| 4 | It stands | / | / | 5 |
| 5 | Terminate | / | / | / |
To the finished battery carry out electric performance test, energy density 252Wh/kg, by 500 times recycle after,
Capacity retention ratio is still up to 96%.
The beneficial effects of the invention are as follows：
(1) preparation method of high energy density cells of the invention carries out first time evacuation after fluid injection, can incite somebody to action
The discharges such as the micro moisture and air that are introduced in injection process avoid causing harmful effect to the performance of battery；
(2) preparation method of high energy density cells of the invention has carried out second of evacuation behaviour after preliminary filling is completed
Make, preliminary filling is formed to the gas generated in SEI membrane process and is discharged, so that it is guaranteed that there is no gas in battery, reduces gas to battery
The influence of performance；
(3) preparation method of high energy density cells of the invention, preliminary filling processing are all made of ladder charging work step with chemical conversion,
Electric current incrementally increases, to ensure that the SEI films to be formed are uniform and fine and close；
(4) battery prepared by the present invention, energy density reaches 250Wh/kg or more, while having excellent multiplying power and cycle
Performance.
The above is the preferred embodiment of the present invention, it should be noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (10)
1. a kind of preparation method of high energy density cells, which is characterized in that include the following steps：
S1. processing is packaged to positive and negative anodes pole piece using aluminum plastic film and obtains packaging electric core；
S2. fluid injection sealing is carried out to the battery core；
S3. first time evacuation is carried out to product after fluid injection；
S4. preliminary filling processing is carried out to obtained product；
S5. second of evacuation is carried out to product；
S6. finished battery is obtained after chemical conversion, partial volume.
2. a kind of preparation method of high energy density cells according to claim 1, which is characterized in that the step S1 with
Further include between step S2：Baking processing is carried out to battery core.
3. a kind of preparation method of high energy density cells according to claim 2, which is characterized in that the step S1 it
It is preceding further comprising the steps of：
S01. the preparation of anode sizing agent, negative electrode slurry；
S02. the coating of anode, cathode, coating anode sizing agent obtains positive plate on plus plate current-collecting body, is applied on negative current collector
Cloth negative electrode slurry obtains negative plate；
S03. the roll-in and film-making of positive plate, negative plate；
S04. the baking of positive plate, negative plate；
S05. lamination prepares battery core；
S06. the welding of positive pole ear, negative lug.
4. a kind of preparation method of high energy density cells according to claim 3, which is characterized in that the step S101
It specifically includes：Be sieved after positive active material, positive conductive agent and positive electrode binder are mixed up to it is described just
Pole slurry；It is sieved after negative electrode active material, cathode conductive agent, cathode thickener, negative electrode binder are mixed to obtain the final product
The negative electrode slurry；The viscosity of the anode sizing agent is 3000-8000mPas, and the viscosity of the negative electrode slurry is 2000-
6000mPa·s。
5. a kind of preparation method of high energy density cells according to claim 4, which is characterized in that the positive-active
Substance is the multicomponent material that the nickel content by cladding processing is higher than 60%, and covering is in aluminium oxide, magnesia, zirconium oxide
It is one or more；The positive conductive agent is graphene slurry, carbon nano tube paste, one or more in carbon nano-fiber,
The positive electrode binder is Kynoar or polytetrafluoroethylene (PTFE).
6. a kind of preparation method of high energy density cells according to claim 4, which is characterized in that the negative electrode active
Substance is the mixture of pure natural graphite or natural graphite and artificial graphite, and the cathode thickener is carboxymethyl cellulose
Sodium, the negative electrode binder be butadiene-styrene rubber, polyacrylic resin or polyimides, the cathode conductive agent be conductive black,
Superconduction carbon, electrically conductive graphite, crystalline flake graphite, carbon nanotube or carbon nano-fiber.
7. a kind of preparation method of high energy density cells according to claim 6, which is characterized in that the anode collection
Body is aluminium foil, and thickness is 12-15 μm；The negative current collector is copper foil, and thickness is 6-10 μm；The diaphragm of the battery is vigorous nurse
Stone coated separator, electrolyte is LiPF6 in the electrolyte that the fluid injection uses, in solvent EC, DEC, PC, DMC, EMC at least
The surface density of two kinds of mixture, the positive plate is 30-40mg/cm2, compacted density 3.0-3.6g/cc；The negative plate
Surface density be 15-20mg/cm2, compacted density 1.4-1.7g/cc, the baking temperature of the positive and negative anodes pole piece is 80~130
DEG C, vacuum degree is -0.085~-0.095MPa, and baking time is 12~24 hours；The battery core baking temperature is 50~85 DEG C,
Vacuum degree is -0.085~-0.095MPa, and baking time is 12~48 hours；The preliminary filling processing is all made of ladder with chemical conversion and fills
Electrician walks.
8. a kind of high energy density cells, which is characterized in that using such as claim 1-7 any one of them methods preparation
At.
9. a kind of high energy density cells according to claim 8, which is characterized in that the anode sizing agent is by following quality
The group of percentage is grouped as：Positive active material 90-98%, positive conductive agent 0.5-5%, positive electrode binder 1.5-5%；It is described
Negative electrode slurry is grouped as by the group of following mass percent：Negative electrode active material 90-96%, cathode conductive agent 1-3%, cathode increase
Thick dose of 1-3%, negative electrode binder 2-4%.
10. a kind of high energy density cells according to claim 8, which is characterized in that the positive active material is warp
The nickel content for crossing cladding processing is higher than 60% multicomponent material, and covering is aluminium oxide, magnesia, one kind in zirconium oxide or more
Kind；The negative electrode active material is the mixture of natural graphite or natural graphite and artificial graphite.
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| CN112652830A (en) * | 2020-12-30 | 2021-04-13 | 骆驼集团武汉新能源科技有限公司 | Exhaust method for improving interface of aluminum shell lithium ion battery pole piece |
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