CN104810557B - Preparation method of lithium ion battery - Google Patents
Preparation method of lithium ion battery Download PDFInfo
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- CN104810557B CN104810557B CN201510153394.9A CN201510153394A CN104810557B CN 104810557 B CN104810557 B CN 104810557B CN 201510153394 A CN201510153394 A CN 201510153394A CN 104810557 B CN104810557 B CN 104810557B
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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
- H01M10/05—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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a lithium ion battery. The preparation method mainly comprises the following steps: preparing a lithium-rich naked battery core, generating an initial SEI film, decomposing the initial SEI film, regenerating the SEI film, preparing a finished battery core and the like. The lithium ion battery prepared by using the preparation method can allow the initial SEI film, which is larger in differences of the structure, performance and consistency caused by lithium supplement, to be fully resolved; the SEI film, which is controllable in structure and performance and excellent in consistency, can be formed through secondary formation, so that the battery core is more excellent in capacity and more excellent in cycling performance.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of preparation method of lithium ion battery.
Background technology
Lithium ion battery has the advantages that high-energy-density, high voltage, low self-discharge and lightweight, therefore is widely used
In the various Portable mobile electronic devices such as notebook computer, digital camera, mobile phone, MP3.As Portable movable electronics sets
The standby development to miniaturization, multifunction, people require more and more higher to the energy density of lithium rechargeable battery.Due to lithium from
Sub- battery during chemical conversion needs to form solid electrolyte (SEI) film, so as to consume the Li provided by negative electrode+, bring
The capacitance loss of battery, have impact on the lifting of energy density.For graphite system, chemical conversion first can bring about 10%
Energy loss；For the alloy anode material of some high power capacity, such as silicon substrate, tinbase and Sn～Co～Al composites etc., first
Efficiency even only 60%～80%, has had a strong impact on practical application and the popularization of alloy material.
In order to greatly improve the energy density of battery core, need to improve the coulombic efficiency first of battery core.Therefore it is domestic
Outer expert expands extensive research, and achieves some achievements：The patent of Chinese patent application Publication No. CN1177417A
Using metal lithium sheet to be covered in anode strip (using full wafer foil as collector) surface, then winding makes battery, then fills
The method of note electrolyte prepares rich lithium ion battery.Using the method mend lithium when, due to existing process cannot produce thickness compared with
Thin metal lithium sheet, therefore often lead to the lithium amount lithium amount that far smaller than metal lithium sheet is provided that anode strip can absorb so that
Mend the problems such as lithium is excessive, analysis lithium, cycle performance difference occurs in battery core.The Chinese patent of Publication No. CN103199217A is proposed, is adopted
Anode strip surface is covered in the metal lithium sheet after punching, then winding makes battery, the method for Reperfu- sion electrolyte prepares richness
Lithium ion battery, efficiently solves the problem of the metal lithium sheet that cannot produce sufficiently thin.
But the above improves battery efficiency and then the method that improves battery capacity first by rich lithium means, in electricity
In the preparation process of pond, with the infiltration of electrolyte after fluid injection, rich lithium material and ion channel and electricity between rich lithium electrode, is formed
During subchannel, by by the spontaneous formation solid electrolyte film in rich lithium material grainses surface (SEI films), the film forming mistake of the SEI films
Journey is uncontrollable process, and the SEI films composition of formation and structural integrity are poor, therefore the battery core cycle performance for preparing is poor.
In view of this, it is necessory to develop a kind of new lithium ion battery and preparation method thereof, can not only be to whole battery
System carries out rich lithium, while and the good SEI films of structural behaviour concordance can be formed, finally prepare the electricity of function admirable
Pond.
The content of the invention
It is an object of the invention to：For the deficiencies in the prior art, and a kind of preparation method of the lithium ion battery for providing：
The method mainly include the preparation of the naked battery core of rich lithium, the generation of initial SEI films, initial SEI films decompose, the regeneration of SEI films with
And finished product battery core prepare etc. step.Lithium ion battery is prepared using the method, can be such that due to mending structural behaviour caused by lithium
The larger initial SEI films of concordance gap fully decompose, by it is secondary chemical conversion formed structure and performance it is controllable, concordance it is excellent
SEI films, therefore battery core has more excellent capacity and cycle performance.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of preparation method of lithium ion battery, comprises the steps：
Step 1, the preparation of the naked battery core of rich lithium：Rich lithium material is compounded on anode strip and obtains lithium-rich anode strip, used
Composite pressure is 0.1MPa～50MPa, and the cathode sheets after lithium-rich anode strip and drying, isolating membrane are assembled into naked battery core afterwards,
Electrolyte is injected after entering shell/bag, and sealing afterwards obtains the battery core after fluid injection；
Step 2, the generation of original solid dielectric film (SEI films)：The battery core that step 1 is obtained is at 10 DEG C～100 DEG C
1min～100h is stood, with the infiltration of electrolyte during standing, the rich lithium material and anode active matter of anode surface attachment
The voltage difference existed between matter is facilitated the generation of anode active material particle surface SEI automatically；
Step 3, the decomposition of initial SEI films：The battery core obtained by step 2, apply 0～5MPa face pressure, and 10 DEG C～
At 100 DEG C, (C is battery capacity value, and for example, if battery capacity is 1500mAh, 1C is 1500mA to adopt 0.001C～5C
Electric current) discharge current, be discharged to 2.5V～0V so that the SEI films being initially formed fully decompose；
Step 4, the regeneration of SEI films：The Zhenyang interpolar of the battery core obtained to step 3 is charged chemical conversion, forms structure
And the SEI films that performance is homogeneous；
Step 5, the preparation of finished product battery core：Battery core obtained in step 4 is carried out into shaping, degasification finished product battery core.
Improve as a kind of the of preparation method of lithium ion battery of the present invention, used in the anode strip described in step 1
Anode active material includes at least one in graphite, silicon, oxide and lithium titanate；The collector is continuous collector or many
Hole collector.
Improve as a kind of the of preparation method of lithium ion battery of the present invention, the rich lithium material described in step 1 is to be
Anode mends the material that lithium provides lithium source, including lithium powder, lithium slurry material, lithium band, punching lithium band and rich lithium Organic substance (such as Isosorbide-5-Nitrae-butyl
Two lithiums, two lithium of 1,6- hexyls etc.) at least one.
Improve as a kind of the of preparation method of lithium ion battery of the present invention, the composite pressure used by step 1 is
0.5MPa～10MPa；It is described enter shell is into aluminum hull or enters box hat, it is into aluminum plastic film bag or rustless steel membrane bag to enter bag.
Improve as a kind of the of preparation method of lithium ion battery of the present invention, additive level in electrolyte described in step 1
1.0 times～2.0 times of additive level in electrolyte are noted by non-lipid lithium cell, preferably 1.1 times～1.8 times, the electrolysis
Solution additive includes FB, VC, PS, FEC, AND etc.；In the noted electrolyte of the non-lipid lithium cell, additive total content is 0.1%
～30%, in electrolyte described in step 1, additive total content is 0.2%～60%, preferably 0.11%～54%.
Improve as a kind of the of preparation method of lithium ion battery of the present invention, the mode for injecting electrolyte in step 1 is normal
Pressure injection liquid accelerates infiltration fluid injection, and when the acceleration infiltration fluid injection mode is negative pressure liquid injection, fluid injection, clamping battery core causes liquid level
Naked battery core is not crossed, battery core is extruded after fluid injection or naked battery core is soaked in electrolyte.
To improve as a kind of the of preparation method of lithium ion battery of the present invention, the temperature stood described in step 2 is 20 DEG C～
85 DEG C, the persistent period of standing is 10min～50h.
Improve as a kind of the of preparation method of lithium ion battery of the present invention, described in step 3 to the face pressure that battery core applies be
0.1MPa～2MPa, temperature are 20 DEG C～85 DEG C, and discharge current is 0.01C～2C, is discharged to 2.0～0V.
Improve as a kind of the of preparation method of lithium ion battery of the present invention, described in step 3 to the face pressure that battery core applies be
0.2MPa～1.5MPa, temperature are 30 DEG C～80 DEG C, and discharge current is 0.01C～1C, is discharged to 1.5V～0V.
Improve as a kind of the of preparation method of lithium ion battery of the present invention, the mode of the chemical conversion in step 4 is generalization
Into or fixture chemical conversion；The common chemical synthesis technology is that battery core is placed in burn-in board, at 20 DEG C～60 DEG C, using 0.01C～
The electric current of 0.5C charges to 3%～80%SOC；The fixture chemical synthesis technology is the face pressure for applying 0.1MPa～5MPa to battery core,
At 20 DEG C～100 DEG C, (i.e. charged state, 10%SOC are to charge to 3%～95%SOC using the electric current of 0.1C～10C
The state that battery charges when making 10% capacity).
It is an advantage of the current invention that：By carrying out the decomposition and reformation process of SEI films to rich lithium battery, by shape during rich lithium
Into structure and the SEI films of consistency of performance difference decompose, then structure is re-formed by secondary formation process and performance is consistent
The good SEI films of property, therefore battery core has more excellent capacity and cycle performance.
Specific embodiment
The present invention and its advantage are described in detail with reference to specific embodiment, but the embodiment party of the present invention
Formula not limited to this.
Comparative example 1, the preparation of the naked battery core of rich lithium：Silicon-carbon complex is selected to be anode active material, with conductive agent, bonding agent
And deionized water is uniformly mixing to obtain slurry, be coated on copper current collector afterwards, cold pressing, slitting, welding, after rubberizing drying treat
With；Cobalt acid lithium is selected to be that cathode active material is uniformly mixing to obtain slurry with conductive agent, bonding agent and N-methyl Topiramate Los oxazolidinone, it
After be coated on aluminum fluid, cold pressing, slitting, welding, dried for standby after rubberizing；With metal lithium bands as rich lithium source, according to full battery
Efficiency is that 95% capacity relationship selects lithium band first, afterwards using the face pressure of 2MPa by lithium band compound anode table after the drying
Face；Above-mentioned cathode sheets, lithium-rich anode strip winding are obtained into naked battery core.
The formation of SEI films：Above-mentioned naked battery core is packaged in aluminum plastic film the battery core obtained after closedtop；According to EC:DEC:PC:
VC:FEC=35:35:30:1:The relationship between quality of 5 (VC, FEC are additive), selection LiPF6 are that lithium salts configuration electrolyte is standby；
Vacuum Package in the battery core that above-mentioned electrolyte is injected after above-mentioned closedtop；Placing 24h in 35 DEG C of environment causes electrolyte abundant
Infiltration；During with the infiltration of electrolyte, due to presence between the rich lithium material and anode active material of anode surface attachment
Voltage difference, is promoted the generation of anode active material particle surface SEI automatically；
It is prepared by finished product battery core：Battery core obtained above is carried out into shaping, degasification finished product battery core.
Embodiment 1, from unlike comparative example 1, the present embodiment comprises the steps：
The preparation of the naked battery core of rich lithium：With comparative example 1.
The formation of initial SEI films：Above-mentioned naked battery core is packaged in aluminum plastic film the battery core obtained after closedtop；According to EC:
DEC:PC:VC:FEC=35:35:30:1.4:The relationship between quality of 7 (VC, FEC are additive), selection LiPF6 are lithium salts configuration electricity
Solution liquid is standby；Vacuum Package in the battery core that above-mentioned electrolyte is injected after above-mentioned closedtop；24h is placed in 35 DEG C of environment causes electricity
Solution liquid fully infiltrates；During with the infiltration of electrolyte, due to the rich lithium material and anode active material of anode surface attachment
Between there is voltage difference, promoted automatically the generation of anode active material particle surface SEI；.
Initial SEI films decompose：The battery core of the initial SEI films of formation to preparing applies 1.0MPa face pressures, is placed in 70 DEG C
At a temperature of, using 0.5C current discharges to 1.5V so that the SEI films being initially formed fully decompose.
The regeneration of SEI films：At 45 DEG C, pressure is not applied to battery core surface, using 0.02C electric currents to battery core charging 10%
The electricity of SOC, then with 0.5C charging 30%SOC so that battery core re-forms SEI films.
It is prepared by finished product battery core：With comparative example 1.
Remaining is identical with comparative example 1, repeats no more.
Embodiment 2, as different from Example 1, the present embodiment comprises the steps：
Initial SEI films decompose：The battery core of the initial SEI films of formation to preparing applies 0MPa face pressures, be placed in 20 DEG C it is warm
Under degree, using 0.01C current discharges to 2.5V so that the SEI films being initially formed fully decompose.
The regeneration of SEI films：At 20 DEG C, 0.1MPa pressure is applied to battery core surface, battery core is charged using 0.01C electric currents
The electricity of 3%SOC, then with 1C charging 30%SOC so that battery core re-forms SEI films.
Remaining is repeated no more with embodiment 1.
Embodiment 3, as different from Example 1, the present embodiment comprises the steps：
Initial SEI films decompose：The battery core of the initial SEI films of formation to preparing applies 0.1MPa face pressures, is placed in 30 DEG C
At a temperature of, using 0.1C current discharges to 2V so that the SEI films being initially formed fully decompose.
The regeneration of SEI films：At 60 DEG C, 0MPa pressure is applied to battery core surface, battery core is charged using 0.5C electric currents
The electricity of 80%SOC so that battery core re-forms SEI films.
Remaining is repeated no more with embodiment 1.
Embodiment 4, as different from Example 1, the present embodiment comprises the steps：
Initial SEI films decompose：The battery core of the initial SEI films of formation to preparing applies 0.2MPa face pressures, is placed in 10 DEG C
At a temperature of, using 0.05C current discharges to 1.0V so that the SEI films being initially formed fully decompose.
The regeneration of SEI films：At 100 DEG C, 0.4MPa pressure is applied to battery core surface, battery core is charged using 10C electric currents
The electricity of 20%SOC so that battery core re-forms SEI films.
Remaining is repeated no more with embodiment 1.
Embodiment 5, as different from Example 1, the present embodiment comprises the steps：
Initial SEI films decompose：The battery core of the initial SEI films of formation to preparing applies 1.5MPa face pressures, is placed in 100 DEG C
At a temperature of, 0V is discharged to 0V, then with 1C using 5C current discharges so that the SEI films being initially formed fully decompose.
The regeneration of SEI films：At 50 DEG C, 5MPa pressure is applied to battery core surface, battery core is charged using 0.5C electric currents
The electricity of 95%SOC so that battery core re-forms SEI films.
Remaining is repeated no more with embodiment 1.
Embodiment 6, as different from Example 1, the present embodiment comprises the steps：
Initial SEI films decompose：The battery core of the initial SEI films of formation to preparing applies 2MPa face pressures, be placed in 85 DEG C it is warm
Under degree, 0V is discharged to 0V, then with 0.5C using 2C current discharges so that the SEI films being initially formed fully decompose.
The regeneration of SEI films：At 80 DEG C, 1.5MPa pressure is applied to battery core surface, battery core is charged using 4C electric currents
The electricity of 60%SOC so that battery core re-forms SEI films.
Remaining is repeated no more with embodiment 1.
Embodiment 7, as different from Example 1, the present embodiment comprises the steps：
Initial SEI films decompose：The battery core of the initial SEI films of formation to preparing applies 0.8MPa face pressures, is placed in 80 DEG C
At a temperature of, 0V is discharged to 0.5V, then with 0.1C using 1C current discharges so that the SEI films being initially formed fully decompose.
The regeneration of SEI films：At 75 DEG C, 0.9MPa pressure is applied to battery core surface, battery core is charged using 2C electric currents
The electricity of 66%SOC so that battery core re-forms SEI films.
Remaining is repeated no more with embodiment 1.
Embodiment 8, as different from Example 1, the present embodiment comprises the steps：
The preparation of the naked battery core of rich lithium：Silicon-carbon complex is selected to be anode active material, with conductive agent, bonding agent and deionization
Water is uniformly mixing to obtain slurry, is coated on copper current collector afterwards, cold pressing, slitting, welding, dried for standby after rubberizing；Select cobalt
Sour lithium is that cathode active material is uniformly mixing to obtain slurry with conductive agent, bonding agent and N-methyl Topiramate Los oxazolidinone, is coated in afterwards
On aluminum fluid, cold pressing, slitting, welding, dried for standby after rubberizing；With metal lithium bands as rich lithium source, according to full battery efficiency first
Capacity relationship for 95% selects lithium band, afterwards using the face pressure of 0.1MPa by lithium band compound anode surface after the drying；Will
Above-mentioned cathode sheets, lithium-rich anode strip winding obtain naked battery core.
The formation of SEI films：Above-mentioned naked battery core is packaged in aluminum plastic film the battery core obtained after closedtop；According to EC:DEC:PC:
VC:FEC=35:35:30:1:The relationship between quality of 5 (VC, FEC are additive), selection LiPF6 are that lithium salts configuration electrolyte is standby；
Vacuum Package in the battery core that above-mentioned electrolyte is injected after above-mentioned closedtop；Placing 100h in 10 DEG C of environment causes electrolyte abundant
Infiltration；During with the infiltration of electrolyte, due to presence between the rich lithium material and anode active material of anode surface attachment
Voltage difference, is promoted the generation of anode active material particle surface SEI automatically；
Remaining is repeated no more with embodiment 1.
Embodiment 9, as different from Example 1, the present embodiment comprises the steps：
The preparation of the naked battery core of rich lithium：Graphite anode active material is selected, it is equal with the stirring of conductive agent, bonding agent and deionized water
It is even to obtain slurry, be coated on copper current collector afterwards, cold pressing, slitting, welding, dried for standby after rubberizing；Select LiFePO4 be
Cathode active material is uniformly mixing to obtain slurry with conductive agent, bonding agent and N-methyl Topiramate Los oxazolidinone, is coated in aluminum fluid afterwards
On, cold pressing, slitting, welding, dried for standby after rubberizing；With metallic lithium powder as rich lithium source, according to full battery first efficiency be 94%
Capacity relationship select lithium band, afterwards using the face pressure of 0.5MPa by lithium band compound anode surface after the drying；By above-mentioned the moon
Pole piece, lithium-rich anode strip winding obtain naked battery core.
The formation of SEI films：Above-mentioned naked battery core is packaged in aluminum plastic film the battery core obtained after closedtop；According to EC:DEC:PC:
VC:FEC=35:35:30:1.1:The relationship between quality of 5.5 (VC, FEC are additive), selection LiPF6 are that lithium salts configures electrolyte
It is standby；(fluid injection mode is for Vacuum Package in the battery core that above-mentioned electrolyte is injected after above-mentioned closedtop：Negative pressure liquid injection, while fluid injection
When clamping battery core keep sufficiently high electrolyte liquid level, and battery core is extruded after the completion of fluid injection so as to accelerate to be electrolysed immersion
Profit)；Placing 1min in 100 DEG C of environment causes electrolyte fully to infiltrate；During with the infiltration of electrolyte, due to anode table
There is voltage difference between the rich lithium material and anode active material of face attachment, promoted automatically anode active material particle surface
The generation of SEI；
Remaining is repeated no more with embodiment 1.
Embodiment 10, as different from Example 1, the present embodiment comprises the steps：
The preparation of the naked battery core of rich lithium：Selection lithium titanate-silicon compound be anode active material, with conductive agent, bonding agent and
Deionized water is uniformly mixing to obtain slurry, is coated on copper current collector afterwards, cold pressing, slitting, welding, dried for standby after rubberizing；
Cobalt acid lithium is selected to be that cathode active material is uniformly mixing to obtain slurry with conductive agent, bonding agent and N-methyl Topiramate Los oxazolidinone, afterwards
Be coated on aluminum fluid, cold pressing, slitting, welding, dried for standby after rubberizing；With metal lithium bands as rich lithium source, according to full battery head
Secondary efficiency is that 95% capacity relationship selects lithium band, afterwards using the face pressure of 10MPa by lithium band compound anode table after the drying
Face；Above-mentioned cathode sheets, lithium-rich anode strip winding are obtained into naked battery core.
The formation of SEI films：According to EC:DEC:PC:VC:FEC=35:35:30:1.8:The matter of 9 (VC, FEC are additive)
Magnitude relation, selection LiPF6 are that lithium salts configuration electrolyte is standby；Above-mentioned naked battery core is soaked in above-mentioned electrolyte, while control
Electrolyte temperature is 85 DEG C, and soak time causes electrolyte fully to infiltrate for 10min, then naked battery core is packaged in aluminum plastic film；
During with the infiltration of electrolyte, due to there is voltage between the rich lithium material and anode active material of anode surface attachment
Difference, is promoted the generation of anode active material particle surface SEI automatically；
Remaining is repeated no more with embodiment 1.
Embodiment 11, as different from Example 1, the present embodiment comprises the steps：
The preparation of the naked battery core of rich lithium：Selection lithium titanate-silicon compound be anode active material, with conductive agent, bonding agent and
Deionized water is uniformly mixing to obtain slurry, is coated on copper current collector afterwards, cold pressing, slitting, welding, dried for standby after rubberizing；
Cobalt acid lithium is selected to be that cathode active material is uniformly mixing to obtain slurry with conductive agent, bonding agent and N-methyl Topiramate Los oxazolidinone, afterwards
Be coated on aluminum fluid, cold pressing, slitting, welding, dried for standby after rubberizing；With metal lithium bands as rich lithium source, according to full battery head
Secondary efficiency is that 95% capacity relationship selects lithium band, afterwards using the face pressure of 50MPa by lithium band compound anode table after the drying
Face；Above-mentioned cathode sheets, lithium-rich anode strip winding are obtained into naked battery core.
The formation of SEI films：According to EC:DEC:PC:VC:FEC=35:35:30:2:The quality of 10 (VC, FEC are additive)
Relation, selection LiPF6 are that lithium salts configuration electrolyte is standby；Above-mentioned naked battery core is soaked in above-mentioned electrolyte, while controlling electricity
Solution liquid temp is 20 DEG C, and soak time causes electrolyte fully to infiltrate for 50h, then naked battery core is packaged in aluminum plastic film；Process
In with the infiltration of electrolyte, due to there is voltage difference between the rich lithium material and anode active material of anode surface attachment, general
Automatically promote the generation of anode active material particle surface SEI；
Remaining is repeated no more with embodiment 1.
Characterize and test：
Volume test：To comparative example 1 and the battery core in 1～embodiment of embodiment 11,100 are respectively taken, in 35 DEG C of environment
Volume test is carried out to battery core by following flow process：Stand 3min；0.5C constant-current charges are to 4.2V, constant-voltage charge to 0.05C；Stand
3min；0.5C constant-current discharges obtain discharge capacity D0 first to 3.0V；Volume test is completed after standing 3min, calculates each afterwards
The meansigma methodss of the capacity of 100 battery cores in group, and calculate the Sigma of capacity；Acquired results are shown in Table 1.
Loop test：To comparative example 1 and the battery core in 1～embodiment of embodiment 11,5 are respectively taken, is entered in 35 DEG C of environment
Row loop test, flow process is：Stand 3min；0.5C constant-current charges are to 4.2V, constant-voltage charge to 0.05C；Stand 3min；0.5C is permanent
Stream is discharged to 3.0V and obtains discharge capacity first, and the average size for calculating per group of 5 battery cores afterwards is D0；After standing 3min,
The above-mentioned flow process of Posterior circle measure battery core capacity within 500 weeks, calculate afterwards per group of 5 battery cores average size be D499, then battery core hold
Amount conservation rate η=D499/D0* 100%, acquired results are shown in Table 1.
The electrical property table of lithium ion battery prepared by the method for table 1, comparative example and embodiment
Can be obtained by table 1, when preparing lithium ion battery using the method for the present invention, the battery core for obtaining has higher capacity,
And capacity distribution is more concentrated；In addition, the cycle performance of the battery core of present invention preparation is more preferable.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is changed.Therefore, above-mentioned specific embodiment is the invention is not limited in, every those skilled in the art exist
On the basis of the present invention it is done it is any conspicuously improved, replace or modification belongs to protection scope of the present invention.This
Outward, although some specific terms used in this specification, these terms merely for convenience of description, not to the present invention
Constitute any restriction.
Claims (10)
1. a kind of preparation method of lithium ion battery, it is characterised in that comprise the steps：
Step 1, the preparation of the naked battery core of rich lithium：Rich lithium material is compounded on anode strip and obtains lithium-rich anode strip, what is used is compound
Pressure be 0.1MPa～50MPa, afterwards by lithium-rich anode strip with drying after cathode sheets, isolating membrane be assembled into naked battery core, enter shell/
Electrolyte is injected after bag, sealing afterwards obtains the battery core after fluid injection；
Step 2, the generation of initial SEI films：The battery core that step 1 is obtained stands 1min～100h at 10 DEG C～100 DEG C, stands
During with the infiltration of electrolyte, the voltage difference general existed between the rich lithium material and anode active material of anode surface attachment
Automatically facilitate the generation of anode active material particle surface SEI；
Step 3, the decomposition of initial SEI films：The battery core obtained to step 2, applies the face pressure of 0～5MPa, and at 10 DEG C～100 DEG C
Under, using the discharge current of 0.001C～5C, it is discharged to 2.5V～0V so that the SEI films being initially formed fully decompose；
Step 4, the regeneration of SEI films：The negative and positive interpolar of the battery core obtained to step 3 is charged chemical conversion, forms structure and property
The homogeneous SEI films of energy；
Step 5, the preparation of finished product battery core：Battery core obtained in step 4 is carried out into shaping, degasification finished product battery core.
2. the preparation method of the lithium ion battery described in a kind of claim 1, it is characterised in that in the anode strip described in step 1
The anode active material for being used includes at least one in graphite, silicon, oxide and lithium titanate.
3. a kind of preparation method of the lithium ion battery described in claim 1, it is characterised in that the rich lithium material described in step 1
For the material that lithium provides lithium source can be mended for anode, including at least in lithium powder, lithium slurry material, lithium band and rich lithium Organic substance
Kind.
4. a kind of preparation method of the lithium ion battery described in claim 1, it is characterised in that the compound pressure used by step 1
Power is 0.5MPa～10MPa；It is described enter shell is into aluminum hull or enters box hat, it is into aluminum plastic film bag or stainless steel membrane bag to enter bag.
5. the preparation method of the lithium ion battery described in a kind of claim 1, it is characterised in that add in electrolyte described in step 1
Plus agent content is noted 1.0 times～2.0 times of additive level in electrolyte by non-lipid lithium cell.
6. the preparation method of the lithium ion battery described in a kind of claim 1, it is characterised in that inject electrolyte in step 1
Mode is normal pressure fluid injection or accelerates infiltration fluid injection, and the acceleration infiltration fluid injection mode clamps battery core when being negative pressure liquid injection, fluid injection
So that liquid level did not had naked battery core, and battery core was extruded after fluid injection or naked battery core is soaked in electrolyte.
7. a kind of preparation method of the lithium ion battery described in claim 1, it is characterised in that the temperature stood described in step 2
For 20 DEG C～85 DEG C, the persistent period of standing is 10min～50h.
8. the preparation method of the lithium ion battery described in a kind of claim 1, it is characterised in that battery core is applied described in step 3
Face pressure be 0.1MPa～2MPa, temperature be 20 DEG C～85 DEG C, discharge current be 0.01C～2C, be discharged to 2.0～0V.
9. the preparation method of the lithium ion battery described in a kind of claim 8, it is characterised in that battery core is applied described in step 3
Face pressure be 0.2MPa～1.5MPa, temperature be 30 DEG C～80 DEG C, discharge current be 0.01C～1C, be discharged to 1.5V～0V.
10. a kind of preparation method of the lithium ion battery described in claim 1, it is characterised in that the mode of the chemical conversion in step 4
For common chemical conversion or fixture chemical conversion；The common chemical synthesis technology is that battery core is placed in burn-in board, at 20 DEG C～60 DEG C, is used
The electric current of 0.01C～0.5C charges to 3%～80%SOC；The fixture chemical synthesis technology is to apply 0.1MPa～5MPa to battery core
Face pressure, at 20 DEG C～100 DEG C, charge to 3%～95%SOC using the electric current of 0.1C～10C.
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| CN106785052B (en) * | 2015-11-23 | 2020-07-17 | 天津荣盛盟固利新能源科技有限公司 | Formation method of lithium titanate battery |
| CN111261960B (en) * | 2017-04-17 | 2021-01-29 | 青岛九环新越新能源科技股份有限公司 | Method for constructing stable solid interface on surface of positive electrode of sulfur-based or selenium-based battery |
| KR102246632B1 (en) | 2017-07-11 | 2021-04-30 | 주식회사 엘지화학 | Method for manufacturing the lithium metal battery |
| CN109309265A (en) * | 2017-07-29 | 2019-02-05 | 深圳格林德能源有限公司 | A kind of smooth improvement chemical synthesis technology of high voltage polymer Li-ion battery |
| KR102038669B1 (en) | 2018-01-11 | 2019-10-30 | 주식회사 엘지화학 | Method for manufacturing the lithium metal secondary battery including lithium electrode |
| CN108933047A (en) * | 2018-07-17 | 2018-12-04 | 中国科学院过程工程研究所 | A kind of prelithiation gel electrolyte and preparation method thereof for lithium-ion capacitor |
| CN110911732B (en) * | 2018-09-16 | 2021-12-14 | 深圳格林德能源集团有限公司 | Long-life high-capacity silicon negative electrode lithium ion battery |
| CN111769332B (en) * | 2020-06-29 | 2021-12-14 | 合肥国轩高科动力能源有限公司 | Formation method of pre-lithium battery and pre-lithiation lithium ion battery |
| CN113363669B (en) * | 2021-06-23 | 2023-02-28 | 天津市捷威动力工业有限公司 | Composite diaphragm, lithium ion battery comprising composite diaphragm, and preparation method and application of composite diaphragm |
| CN114388891B (en) * | 2021-11-16 | 2024-03-19 | 中国科学院电工研究所 | Pre-lithium intercalation method and manufacturing method of lithium ion energy storage device |
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| CN102610861A (en) * | 2012-03-07 | 2012-07-25 | 宁德新能源科技有限公司 | Method for preparing lithium ion battery |
| US8999584B2 (en) * | 2013-03-15 | 2015-04-07 | GM Global Technology Operations LLC | Method for pre-lithiation of the negative electrode in lithium ion batteries |
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