CN104752752B - The preparation method of the naked battery core of lithium ion battery and the lithium ion battery containing the naked battery core - Google Patents
The preparation method of the naked battery core of lithium ion battery and the lithium ion battery containing the naked battery core Download PDFInfo
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- CN104752752B CN104752752B CN201510152380.5A CN201510152380A CN104752752B CN 104752752 B CN104752752 B CN 104752752B CN 201510152380 A CN201510152380 A CN 201510152380A CN 104752752 B CN104752752 B CN 104752752B
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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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 technical field of lithium ion, the naked battery core of more particularly to a kind of lithium ion battery：Including cathode sheets, barrier film and anode strip, the barrier film is between cathode sheets and anode strip；Characterized in that, the barrier film has the composite isolated film of the porous structure layer of rich lithium material composition for surface recombination, and the rich lithium material porous structure layer is between barrier film and negative electrode.The lithium ion battery prepared using naked battery core of the invention, can effectively slow down/suppress in electrolyte impregnation process, lithium in rich lithium material layer is internally embedded to cathode active material particle, so as to destroy cathode active material grain structure, and reduce/eliminate the generation of the SEI films of anode interior structural behaviour uniformity difference；The more excellent rich lithium ion battery of final prepared capacity, cycle performance.
Description
Technical field
The invention belongs to technical field of lithium ion, the naked battery core of more particularly to a kind of lithium ion battery and contain the naked electricity
The preparation method of the lithium ion battery of core.
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
For to miniaturization, the development of 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. are imitated first
Rate 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, are 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 uniformity 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 the naked battery core of a kind of lithium ion battery for providing：Including
Cathode sheets, barrier film and anode strip, the barrier film is between cathode sheets and anode strip；The barrier film has for surface recombination
The composite isolated film of the porous structure layer of rich lithium material composition, and the rich lithium material porous structure layer in barrier film and negative electrode it
Between.The lithium ion battery prepared using naked battery core of the invention, can effectively be slowed down/be suppressed in electrolyte impregnation process, rich
Lithium in lithium material layer is internally embedded to cathode active material particle, so as to destroy cathode active material grain structure, and reduce/
Eliminate the generation of the SEI films of anode interior structural behaviour uniformity difference；The more excellent rich lithium of final prepared capacity, cycle performance
Lithium ion battery.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of naked battery core of lithium ion battery, including cathode sheets, barrier film and anode strip, the barrier film is between the negative electrode
Between piece and the anode strip；The barrier film has the compound isolation of the porous structure layer by rich lithium material composition for surface recombination
Film, and the porous structure layer is between the barrier film and the cathode sheets.
Improve as one kind of the naked battery core of lithium ion battery of the present invention, the cathode sheets are by the moon containing cathode active material
Pole coating and cathode current collector composition；The anode strip is by the anodic coating containing anode active material and anode collector group
Into；Described rich lithium material provide the material of lithium source to mend lithium for electrode, including lithium powder, lithium slurry material, lithium band, punch lithium
At least one of band, rich lithium organic matter (such as two lithium of 1,4- butyl, two lithium of 1,6- hexyls etc.).
As the naked battery core of lithium ion battery of the present invention one kind improve, the cathode active material include lithium and cobalt oxides,
Lithium nickel oxide, lithium manganese oxide, oxide/lithium ferrite, lithium-barium oxide, sulphur or sulfide, ternary or multiple elements design compound and
At least one in polyanion cathode material；The anode active material includes material with carbon element, carbon compound and non-carbon material
In at least one.
Improve as one kind of the naked battery core of lithium ion battery of the present invention, the barrier film is with loose structure, ion
The self-supported membrane of conduct electrons insulation, including it is polypropylene, polyethylene, copolymerization second propylene, plastic of poly vinyl acetate copolymer, poly-
At least one in vinylidene, copolymerization fluoro ethyl propene, polyamide and polyimides；Its thickness h is 2um～50um.
Improve as one kind of the naked battery core of lithium ion battery of the present invention, the equivalent bore dia of the porous structure layer is (equivalent
Bore dia referred to when hole area is converted into an area of a circle, the diameter of a circle) less than 4cm；Company between two bore edges
Continuous richness lithium layer width is less than 4cm.
Improve as one kind of the naked battery core of lithium ion battery of the present invention, the equivalent diameter of the porous structure layer is less than
2cm；Continuous rich lithium layer width between two bore edges is less than 2cm.
Improve as one kind of the naked battery core of lithium ion battery of the present invention, it is characterised in that：The barrier film is more with described
Pore structure layer carries out compound tense, and composite force is 0.01MPa～10MPa；The complex method is that barrier film one side is compound or two-sided
It is compound.
Improve as one kind of the naked battery core of lithium ion battery of the present invention, in the composite isolated film, barrier film is without by rich lithium
Layer puncture area or by rich lithium layer puncture site, and region is stabbed by rich lithium layer on barrier film or maximum depth a little is stabbed by rich lithium layer
Degree is not more than (h-1) um；The side of the compound rich lithium material of the barrier film can arrange ceramic coating, PVDF coatings or pottery
Porcelain-PVDF coatings.
Present invention additionally comprises a kind of method for preparing lithium ion battery using above-mentioned naked battery core, it is characterised in that include as
Lower step：
Step 1, the preparation of composite isolated film：Rich lithium material is pre-processed, to obtain the burr at least one face/convex
Porous richness lithium layer of the height of point less than (h-1) um, afterwards will be the barrier film after drying multiple with the pretreatment face of rich lithium material
Close, it is 0.01MPa～10MPa to be combined face pressure, obtains composite isolated film, wherein, thickness of the h for barrier film；
Step 2, battery core to be changed reach preparation：Cathode sheets, anode after the composite isolated film that step 1 is obtained and drying
Piece assembling obtains naked battery core, wherein, porous richness lithium layer injects electrolyte liquid after entering shell/bag between cathode sheets and barrier film,
Stand；
Step 3, the generation of SEI films：The battery core that the Jing electrolyte obtained to step 2 fully infiltrates is melted into, chemical conversion temperature
Spend for 10 DEG C～90 DEG C, charging current be 0.01C～5C (C is battery capacity value, for example, if battery capacity is 1500mAh,
1C is the electric current of 1500mA), it is 0～0.5MPa to the pressure that battery core applies during chemical conversion, charging SOC is charged state, 10%
SOC be battery charge system 10% capacity when state) for 3%～90%；
Step 4, embedding lithium：The battery core that obtains to step 3 applies the face pressure of 0.5MPa～5.0MPa so that rich lithium material layer with
The surface for forming the anode strip after SEI films is fully contacted, to form electron channel, due to existing between rich lithium material layer and anode
Electrical potential difference, the lithium in rich lithium material layer are embedded in spontaneous in anode active material layer, final to realize mending lithium effect；
Step 5, the making 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, in step 1, the rich lithium material is carried out pre-
Process, to obtain porous richness lithium layer of the height of at least one face burr/salient point less than (h-2) um, the face pressure of compound tense is
0.1MPa～3Mpa；It is 0.5MPa～2.0MPa to apply face pressure described in step 4 to battery core, and temperature is 20 DEG C～100 DEG C, and the time is
10min～48h.
Compared with traditional naked core strueture, the lithium ion battery of the naked battery core preparation of the present invention can effectively slow down/press down
Make in electrolyte impregnation process, the lithium in rich lithium material layer is internally embedded to cathode active material particle, destroy cathode activity
Material grainses structure, and reduce/eliminate anode interior structural behaviour uniformity difference SEI films generation (because such directly connecing
Tactile process of intercalation is uncontrollable process)；Meanwhile, flow process is melted into by controllable charging, sufficient anode active matter is being infiltrated
Matter surface forms the homogeneous SEI films of structure and property；After SEI films are formed by controllable charging process, then battery core is applied to press
Power so that be fully contacted between rich lithium material layer and cathode active material, forms electronics and leads to, negative electrode and rich lithium material layer it
Between electrical potential difference driving under, lithium source in rich lithium material layer is spontaneous to be embedded between cathode active material；Finally obtain appearance
The more excellent rich lithium ion battery of amount, 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 compound 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 aluminium 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 negative electrode table after the drying
Face；Above-mentioned anode strip, rich lithium cathode sheets winding are obtained into naked battery core.
Embedding lithium：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 LiPF6It is standby for lithium salts configuration electrolyte；Will be above-mentioned
Vacuum Package in battery core after the above-mentioned closedtop of electrolyte injection；24h is placed in 35 DEG C of environment causes electrolyte fully to infiltrate；Cross
With the infiltration of electrolyte in journey, due to there is voltage difference between the rich lithium material and cathode active material of cathode surface attachment,
Automatically the lithium metal in rich lithium material is promoted to be internally embedded to cathode active material particle；
It is prepared by finished product battery core：Battery core obtained above is carried out into shaping, degasification finished product battery core.
Comparative example 2, the preparation of the naked battery core of rich lithium：Silicon-carbon compound 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 aluminium fluid, cold pressing, slitting, welding, dried for standby after rubberizing；With porous metals lithium band as rich lithium source (hole shape
For circle, bore dia is 0.4cm, and the distance between two bore edges (pitch of holes) are 1cm), according to full battery, efficiency is first
95% capacity relationship selects lithium band, afterwards using the face pressure of 2MPa by lithium band compound anode surface after the drying；Will be 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 LiPF6It is standby for lithium salts configuration electrolyte；
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 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 2, the present embodiment is comprised the following steps：
It is prepared by composite isolated film：Select metal lithium bands to be rich lithium material, which is punched, hole shape is circle, Kong Zhi
Footpath is 0.4cm, and pitch of holes is 1cm, then is rolled so that the burr on metal lithium bands is less than 5um；Afterwards with thickness be 12um
Barrier film be combined, be combined face pressure be 1MPa, finally give composite isolated film.
It is prepared by battery core to be changed：Silicon-carbon compound is selected to be anode active material, with conductive agent, bonding agent and deionized water
Be uniformly mixing to obtain slurry, be coated on copper current collector afterwards, cold pressing, slitting, welding, dried for standby after rubberizing；Select cobalt acid
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 aluminium afterwards
On fluid, cold pressing, slitting, welding, dried for standby after rubberizing；Above-mentioned composite isolated film and cathode sheets, anode strip are wound
To naked battery core (porous richness lithium layer is between cathode sheets and barrier film), selection aluminum plastic film is packaging bag, carries out closedtop, note afterwards
Liquid, standing, liquid to be electrolysed obtain battery core to be changed after fully infiltrating.
SEI films are generated：By above-mentioned infiltration sufficient battery core, it is melted at 70 DEG C, applying pressure is 0.05MPa, charge electricity
Flow for 0.2C, charging SOC is 40% so that anode surface forms SEI films.
Embedding lithium：Battery core to above-mentioned formation SEI films, applies the face pressure of 0.8MPa, then stands 8h in being positioned over 60 DEG C of environment,
So that close electron channel between lithium band and cathode sheets, is formed, and now under the electrical potential difference effect between lithium band and negative electrode, gold
Category lithium will carry out benefit lithium to negative electrode in automatically inserting cathode sheets.
Remaining is identical with comparative example 2, repeats no more.
Embodiment 2, as different from Example 1, the present embodiment comprises the steps：
It is prepared by composite isolated film：Select metal lithium bands to be rich lithium material, which is punched, hole shape is circle, Kong Zhi
Footpath is 4cm, and pitch of holes is 4cm, then is rolled so that the burr on metal lithium bands is less than 20um；Afterwards with thickness be 50um
Barrier film be combined, be combined face pressure be 10MPa, finally give composite isolated film.
It is prepared by battery core to be changed：With embodiment 1.
SEI films are generated：By above-mentioned infiltration sufficient battery core, at 90 DEG C be melted into, applyings pressure be 0.5MPa, charging current
For 5C, charging SOC is 60% so that anode surface forms SEI films.
Embedding lithium：Battery core to above-mentioned formation SEI films, applies the face pressure of 5MPa, then stands 1h in being positioned over 100 DEG C of environment,
So that close electron channel between lithium band and cathode sheets, is formed, and now under the electrical potential difference effect between lithium band and negative electrode, gold
Category lithium will carry out benefit lithium to negative electrode in automatically inserting cathode sheets.
Remaining is same as Example 1, repeats no more.
Embodiment 3, as different from Example 1, the present embodiment comprises the steps：
It is prepared by composite isolated film：Select metal lithium bands to be rich lithium material, which is punched, hole shape is circle, Kong Zhi
Footpath is 2cm, and pitch of holes is 2cm, then is rolled so that the burr on metal lithium bands is less than 10um；Afterwards with thickness be 20um
Barrier film be combined, be combined face pressure be 3MPa, finally give composite isolated film.
It is prepared by battery core to be changed：With embodiment 1.
SEI films are generated：By above-mentioned infiltration sufficient battery core, at 85 DEG C be melted into, applyings pressure be 0.1MPa, charging current
For 1C, charging SOC is 50% so that anode surface forms SEI films.
Embedding lithium：Battery core to above-mentioned formation SEI films, applies the face pressure of 2MPa, then stands 4h in being positioned over 70 DEG C of environment, make
Obtain and between lithium band and cathode sheets, form close electron channel, now under the electrical potential difference effect between lithium band and negative electrode, metal
Lithium will carry out benefit lithium to negative electrode in automatically inserting cathode sheets.
Remaining is same as Example 1, repeats no more.
Embodiment 4, as different from Example 1, the present embodiment comprises the steps：
It is prepared by composite isolated film：Select metal lithium bands to be rich lithium material, which is punched, hole shape is square, etc.
Effect bore dia is 0.9cm, and pitch of holes is 1.6cm, then is rolled so that the burr on metal lithium bands is less than 2um；Afterwards with thickness
Spend for 6um barrier film be combined, be combined face pressure be 0.5MPa, finally give composite isolated film.
It is prepared by battery core to be changed：With embodiment 1.
SEI films are generated：By above-mentioned infiltration sufficient battery core, it is melted at 70 DEG C, applying pressure is 0.07MPa, charge electricity
Flow for 0.5C, charging SOC is 40% so that anode surface forms SEI films.
Embedding lithium：Battery core to above-mentioned formation SEI films, applies the face pressure of 1MPa, then stands 48h in being positioned over 20 DEG C of environment,
So that close electron channel between lithium band and cathode sheets, is formed, and now under the electrical potential difference effect between lithium band and negative electrode, gold
Category lithium will carry out benefit lithium to negative electrode in automatically inserting cathode sheets.
Remaining is same as Example 1, repeats no more.
Embodiment 5, as different from Example 1, the present embodiment comprises the steps：
It is prepared by composite isolated film：Select metal lithium bands to be rich lithium material, which is punched, hole shape is triangle, is had
Effect bore dia is 0.1cm, and pitch of holes is 0.5cm, then is rolled so that the burr on metal lithium bands is less than 2um；Select 2um
The barrier film of thickness applies the ceramic layer that a layer thickness is 4um as matrix to its surface, and it is 2um to apply a layer thickness afterwards
PVDF layers obtain the barrier film after ceramics are processed with PVDF, it is compound with above-mentioned porous metals lithium band after drying to obtain compound the isolation
Film, it is 0.01MPa to be combined face pressure.
Which is punched, hole shape is triangle, effective bore dia is 0.1cm, and pitch of holes is 0.5cm, then is rolled
Pressure so that the burr on metal lithium bands is less than 2um；Select the barrier film of 2um thickness as matrix, thick layer is applied to its surface
The ceramic layer for 4um is spent, the PVDF layers that a layer thickness is 2um is applied afterwards and is obtained the barrier film after ceramics are processed with PVDF, dry
Compound with above-mentioned porous metals lithium band after dry to obtain composite isolated film, it is 0.01MPa to be combined face pressure.
It is prepared by battery core to be changed：With embodiment 1.
SEI films are generated：By above-mentioned infiltration sufficient battery core, it is melted at 10 DEG C, applying pressure is 0.04MPa, charge electricity
Flow for 0.01C, charging SOC is 3% so that anode surface forms SEI films.
Embedding lithium：Battery core to above-mentioned formation SEI films, applies the face pressure of 0.5MPa, then stands in being positioned over 40 DEG C of environment
24h so that close electron channel is formed between lithium band and cathode sheets, now the electrical potential difference effect between lithium band and negative electrode
Under, lithium metal will carry out benefit lithium to negative electrode in automatically inserting cathode sheets.
Remaining is same as Example 1, repeats no more.
Embodiment 6, as different from Example 1, the present embodiment comprises the steps：
It is prepared by composite isolated film：The metallic lithium powder that particle diameter is 50um is selected to be rich lithium source；Select the barrier film of 30um thickness
As matrix, the ceramics-PVDF composite beds that a layer thickness is 4um are applied to its surface and obtains the isolation after ceramics-PVDF is processed
Film, metallic lithium powder is uniformly distributed in after drying barrier film surface, then lithium powder is rolled over isolation using the face pressure of 0.8MPa
Film surface forms porous richness lithium layer.
It is prepared by battery core to be changed：Selection graphite is anode active material, equal with the stirring of conductive agent, bonding agent and deionized water
It is even to obtain slurry, be coated on the copper current collector of porous afterwards, cold pressing, slitting, welding, dried for standby after rubberizing；Select phosphoric acid
Iron 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 aluminium fluid, cold pressing, slitting, welding, dried for standby after rubberizing；Above-mentioned composite isolated film is wound with cathode sheets, anode strip
Naked battery core (porous richness lithium layer is between cathode sheets and barrier film) is obtained, is selected rustless steel membrane to be packaging bag, is pushed up afterwards
Envelope, fluid injection, standing, liquid to be electrolysed obtain battery core to be changed after fully infiltrating.
SEI films are generated：By above-mentioned infiltration sufficient battery core, it is melted at 70 DEG C, applying pressure is 0.05MPa, charge electricity
Flow for 0.2C, charging SOC is 90% so that anode surface forms SEI films.
Embedding lithium：Battery core to above-mentioned formation SEI films, applies the face pressure of 0.8MPa, then stands 8h in being positioned over 60 DEG C of environment,
So that close electron channel between lithium band and cathode sheets, is formed, and now under the electrical potential difference effect between lithium band and negative electrode, gold
Category lithium will carry out benefit lithium to negative electrode in automatically inserting cathode sheets.
Remaining is same as Example 1, repeats no more.
Embodiment 7, as different from Example 6, the present embodiment comprises the steps：
It is prepared by composite isolated film：The slurry that the metallic lithium powder configuration that particle diameter is 30um is obtained is selected for rich lithium source；Select
The barrier film of 30um thickness as matrix, its surface is applied the ceramics-PVDF composite beds that a layer thickness is 4um obtain ceramics-
Barrier film after PVDF process, metallic lithium powder is uniformly distributed in after drying barrier film surface (one of surface), then is adopted
Lithium powder is rolled over into barrier film surface with the face pressure of 1MPa and forms porous richness lithium layer.
It is prepared by battery core to be changed：Selection graphite is anode active material, equal with the stirring of conductive agent, bonding agent and deionized water
It is even to obtain slurry, be coated on the copper current collector of porous afterwards, cold pressing, slitting, welding, dried for standby after rubberizing；Select sulphur carbon
Compound is that cathode active material is uniformly mixing to obtain slurry with conductive agent, bonding agent and N-methyl Topiramate Los oxazolidinone, is applied afterwards
On aluminium fluid, cold pressing, slitting, welding, rubberizing, using lithium band richness lithium technology rich lithium is carried out to the sulphur negative electrode for obtaining, treat afterwards
With；By above-mentioned composite isolated film and cathode sheets, anode strip lamination obtain naked battery core (porous richness lithium layer between cathode sheets with isolate
Between film), select rustless steel membrane to be packaging bag, carry out closedtop, fluid injection, standing afterwards, liquid to be electrolysed is treated after fully infiltrating
Chemical conversion battery core.
SEI films are generated：By above-mentioned infiltration sufficient battery core, it is melted at 70 DEG C, applying pressure is 0.05MPa, charge electricity
Flow for 0.2C, charging SOC is 10% so that anode surface forms SEI films.
Embedding lithium：Battery core to above-mentioned formation SEI films, applies the face pressure of 0.8MPa, then stands 8h in being positioned over 60 DEG C of environment,
So that close electron channel between lithium powder and cathode sheets, is formed, and now under the electrical potential difference effect between lithium powder and negative electrode, gold
Category lithium will carry out benefit lithium to negative electrode in automatically inserting cathode sheets.
Remaining is same as Example 6, repeats no more.
Characterize and test：
Volume test：To comparative example 1,2 and the battery core in 1～embodiment of embodiment 6,100 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 mean value of the capacity of 100 battery cores in group, and calculate the Sigma of capacity；Acquired results are shown in Table 1.
Battery core in 100 embodiments 7 is taken, volume test is carried out to battery core by following flow process in 35 DEG C of environment：Stand
3min；0.5C constant-current charges are to 2.8V, constant-voltage charge to 0.05C；Stand 3min；0.5C constant-current discharges are put first to 1.5V
Capacitance D0；Volume test is completed after standing 3min, the mean value of the capacity of 100 battery cores in each group is calculated afterwards, and is counted
Calculate the Sigma of capacity；Acquired results are shown in Table 1.
Loop test：To comparative example 1,2 and the battery core in 1～embodiment of embodiment 6,5 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.
Battery core in 5 embodiments 7 is taken, test is circulated in 35 DEG C of environment, flow process is：Stand 3min；0.5C constant currents
Charge to 2.8V, constant-voltage charge to 0.05C；Stand 3min；0.5C constant-current discharges obtain discharge capacity first, Zhi Houji to 1.5V
The average size for calculating per group of 5 battery cores is D0；Stand 3min after, the above-mentioned flow process of Posterior circle measure battery core capacity within 500 weeks, it
The average size for calculating per group of 5 battery cores afterwards is D499, then battery core capability retention 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
According to table 1, it is found that the battery core performance of comparative example 1 is significantly lower than other groups, this is due to also not taking off lithium
Cobalt acid lithium itself is rich lithium material, when its benefit lithium is continued as, will destroy its crystal structure, and crystal structure will finally occur and collapse
Collapse, capacity plays the problems such as low, cycle performance is poor.Comparative examples 2 can be obtained with embodiment 1～5, using method of the present invention system
During standby lithium ion battery, the battery core for obtaining has higher capacity, and capacity distribution is more concentrated；In addition, prepared by the present invention
The cycle performance of battery core is more preferable.Can be obtained by embodiment 6,7, the method is also practical electric with graphite/LiFePO4 system and lithium sulphur
Pond body system, illustrates that the method has universality.
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 (8)
1. a kind of method for preparing lithium ion battery using naked battery core, the naked battery core include cathode sheets, barrier film and anode strip,
The barrier film is between the cathode sheets and the anode strip；The barrier film has by rich lithium material composition for surface recombination
Porous structure layer composite isolated film, and the porous structure layer is between the barrier film and the cathode sheets, and which is special
Levy and be, the method comprises the steps：
Step 1, the preparation of composite isolated film：Rich lithium material is pre-processed, to obtain the burr/salient point at least one face
Highly less than the porous richness lithium layer of (h-1) μm, the pretreatment face by the barrier film after drying with rich lithium material is combined afterwards, answers
Conjunction face pressure is 0.01MPa～10MPa, obtains composite isolated film, wherein, thickness of the h for barrier film；
Step 2, the preparation of battery core to be changed：Cathode sheets, anode strip assembling after the composite isolated film that step 1 is obtained and drying
Naked battery core is obtained, wherein, porous richness lithium layer between cathode sheets and barrier film is injected electrolyte, is stood after entering shell/bag；
Step 3, the generation of SEI films：The battery core that the Jing electrolyte obtained to step 2 fully infiltrates is melted into, and chemical conversion temperature is
10 DEG C～90 DEG C, charging current is 0.01C～5C, is 0～0.5MPa to the pressure that battery core applies during chemical conversion, and charging SOC is 3%
～90%；
Step 4, embedding lithium：The battery core obtained to step 3 applies the face pressure of 0.5MPa～5.0MPa so that rich lithium material layer and formation
The surface of the cathode sheets of the battery core after SEI films is fully contacted, to form electron channel, due to depositing between rich lithium material layer and negative electrode
Lithium in electrical potential difference, rich lithium material layer is embedded in spontaneous in cathode active material layer, final to realize mending lithium effect；
Step 5, the making of finished product battery core：Battery core obtained in step 4 is carried out into shaping, degasification finished product battery core.
2. a kind of method for preparing lithium ion battery described in claim 1, it is characterised in that：The cathode sheets are by containing negative electrode
The cathode of active material and cathode current collector composition；The anode strip is by the anodic coating containing anode active material and sun
Pole collector composition；Described rich lithium material provide the material of lithium source to mend lithium for electrode, including lithium powder, lithium slurry material,
At least one of lithium band, rich lithium organic matter.
3. a kind of method for preparing lithium ion battery described in claim 2, it is characterised in that：The cathode active material includes
Lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, oxide/lithium ferrite, lithium-barium oxide, sulphur or sulfide, ternary or polynary
At least one in complex chemical compound and polyanion cathode material；The anode active material includes material with carbon element, containing carbon compound
At least one in thing.
4. a kind of method for preparing lithium ion battery described in claim 1, it is characterised in that：The barrier film is with porous
Structure, the insulation of ion conduct electrons self-supported membrane, including polypropylene, polyethylene, copolymerization second propylene, polyvinyl acetate ethene
At least one in ester copolymer, Kynoar, copolymerization fluoro ethyl propene, polyamide and polyimides；Its thickness h be 2 μm～
50μm。
5. a kind of method for preparing lithium ion battery described in claim 1, it is characterised in that：The porous structure layer it is equivalent
Bore dia is less than 4cm；Continuous rich lithium layer width between two bore edges is less than 4cm.
6. a kind of method for preparing lithium ion battery described in claim 1, it is characterised in that：The porous structure layer it is equivalent
Bore dia is less than 2cm；Continuous rich lithium layer width between two bore edges is less than 2cm.
7. a kind of method for preparing lithium ion battery described in claim 1, it is characterised in that：In the composite isolated film, every
From film without by rich lithium layer puncture area or by rich lithium layer puncture site, and region is stabbed by rich lithium layer on barrier film or is pierced by rich lithium layer
The depth capacity of wound point is not more than (h-1) μm；The side of the compound rich lithium material of the barrier film arranges ceramic coating, PVDF and applies
Layer or ceramics-PVDF coatings, wherein, thickness of the h for barrier film.
8. a kind of method for preparing lithium ion battery described in claim 1, it is characterised in that in step 1, to the rich lithium thing
Matter is pre-processed, to obtain the porous richness lithium layer of the height of at least one face burr/salient point less than (h-2) μm, compound tense
Face pressure be 0.1MPa～3MPa；Described in step 4 to battery core apply face pressure be 0.5MPa～2.0MPa, temperature be 20 DEG C～
100 DEG C, the time is 10min～48h.
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| CN106450467A (en) * | 2016-09-07 | 2017-02-22 | 中南大学 | Lithium supplementing method for energy storage device |
| CN107658496A (en) * | 2017-09-29 | 2018-02-02 | 北京卫蓝新能源科技有限公司 | A kind of secondary cell and preparation method thereof |
| CN107845829B (en) * | 2017-10-12 | 2021-06-04 | 北京卫蓝新能源科技有限公司 | Double-layer composite diaphragm battery and lithium supplementing method thereof |
| CN112421128B (en) * | 2019-08-05 | 2021-10-22 | 宁德时代新能源科技股份有限公司 | Lithium ion battery |
| CN112531284B (en) * | 2020-12-14 | 2022-10-14 | 湖北亿纬动力有限公司 | Lithium supplement diaphragm, preparation method thereof and lithium ion battery |
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