CN104752773A - Preparation method of lithium ion battery - Google Patents
Preparation method of lithium ion battery Download PDFInfo
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- CN104752773A CN104752773A CN201510152685.6A CN201510152685A CN104752773A CN 104752773 A CN104752773 A CN 104752773A CN 201510152685 A CN201510152685 A CN 201510152685A CN 104752773 A CN104752773 A CN 104752773A
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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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- 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 a lithium ion battery, and particularly relates to a preparation method of a lithium ion battery. The method mainly comprises the steps of preparing an electrode, preparing a naked cell which is convenient to be infiltrated by an electrolyte, injecting the electrolyte, infiltrating the naked cell, forming a solid electrolyte interface (SEI), and preparing a finished product cell. By utilizing the method to prepare the lithium ion battery, the rapid infiltration of the electrolyte can be realized, and the membrane reaction can be maximally limited by virtue of infiltration, so that after the entire cell is infiltrated, the composition consistency of the electrolyte on the electrode is relatively good, and thus the SEI formed in each area of the cell electrode is good in consistency.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly a kind of preparation method of lithium ion battery.
Background technology
Lithium ion battery has high-energy-density, high voltage, low self-discharge and the advantage such as lightweight, is therefore widely used in the various Portable mobile electronic devices such as notebook computer, digital camera, mobile phone, MP3.Along with Portable mobile electronic device is to development that is miniaturized, multifunction, people require more and more higher to the energy density of lithium rechargeable battery.Because lithium ion battery is in the process changed into, needs to form solid electrolyte (SEI) film, thus the Li provided by negative electrode is provided
+, bring the capacitance loss of battery, have impact on the lifting of energy density.For graphite system, change into the energy loss bringing about 10% first; For the alloy anode material of some high power capacity, as silica-based, tinbase and Sn ~ Co ~ Al composite material etc., efficiency even only has 60% ~ 80% first, has had a strong impact on practical application and the popularization of alloy material.
In order to improve the energy density of battery core greatly, need the coulombic efficiency first improving battery core.Therefore domestic and international expert expands and studies widely, and achieving some achievements: Chinese patent application publication number is that metal lithium sheet is covered anode strip (adopting full wafer foil as collector) surface by the patent employing of CN1177417A, then winding makes battery, and the method for Reperfu-sion electrolyte prepares rich lithium ion battery.When using the method to mend lithium, because existing technique cannot produce the metal lithium sheet of thinner thickness, therefore the lithium amount often causing anode strip to absorb is far smaller than the lithium amount that metal lithium sheet provides, and makes to mend excessive, the battery core of lithium and occurs analysing the problem such as lithium, cycle performance difference.Publication number is that the Chinese patent of CN103199217A proposes, the metal lithium sheet after punching is adopted to cover anode strip surface, then winding makes battery, and the method for Reperfu-sion electrolyte prepares rich lithium ion battery, efficiently solves the problem cannot producing enough thin metal lithium sheet.
But above these improve the method for battery efficiency and then raising battery capacity first by rich lithium means, in cell manufacturing process, along with the infiltration of electrolyte after fluid injection, rich lithium material and when being formed ion channel and electron channel between rich lithium electrode, by by the spontaneous formation solid electrolyte film (SEI film) in rich lithium material grains surface, the film forming procedure of this SEI film is uncontrollable process, formed SEI film composition and structural integrity poor, the battery core cycle performance therefore prepared is poor.
In view of this, a kind of new lithium ion battery of necessary exploitation and preparation method thereof, can not only carry out rich lithium to whole battery system, can form again the good SEI film of structural behaviour consistency simultaneously, finally prepare the battery of function admirable.
Summary of the invention
To the object of the invention is to: for the deficiencies in the prior art, and the preparation method of a kind of lithium ion battery provided: the steps such as the method mainly comprises electrode preparation, prepared by the preparation being convenient to the naked battery core that electrolyte infiltrates, fluid injection infiltration, solid electrolyte film (SEI film) film forming, finished product battery core.The method is used to prepare lithium ion battery, the quick infiltration of electrolyte can be realized, and infiltrate the generation that can be constrained to film reaction to greatest extent, thus after whole battery core is infiltrated, electrode By Electrolysis liquid has good content consistency, thus the good consistency of the SEI film that battery core electrode regional is formed.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for lithium ion battery, comprises the steps:
Step 1, the preparation of rich lithium anode: by the slurry coating containing anode active material in anode collector, obtains after oven dry treating rich lithium anode sheet, then will treat that rich lithium anode sheet and rich lithium material compound obtain rich lithium anode;
Step 2, is convenient to the preparation of naked battery core that electrolyte infiltrates: process the cathode sheets after drying, or use the barrier film after process, then rich lithium anode prepared by cathode sheets, barrier film and step 1 is assembled the naked battery core obtaining being convenient to electrolyte and infiltrate;
Step 3, uses the fluid injection mode fluid injection be convenient to electrolyte and infiltrated: after the naked battery core that step 2 is obtained is entered shell/bag, and carry out acceleration and infiltrate fluid injection, sealing obtains the battery core after fluid injection, leaves standstill 1min ~ 4h afterwards; Whole process control battery core temperature is 0 DEG C ~ 80 DEG C;
Step 4, the control of solid electrolyte film (SEI film) film formation reaction: to leave standstill after battery core apply 0 ~ 4MPa face pressure after, be placed in 10 DEG C ~ 95 DEG C environment 10min ~ 20h, make the lithium in rich lithium material layer enter anode active material inside, form SEI film simultaneously;
Step 5, the preparation of finished product battery core: battery core obtained for step 4 is carried out charge, shaping, degasification obtain finished product battery core.
One as the preparation method of lithium ion battery of the present invention is improved, and the anode active material described in step 1 comprises at least one in graphite, silicon, oxide and lithium titanate; Described collector is continuum fluid or porous current collector.
One as the preparation method of lithium ion battery of the present invention is improved, rich lithium material described in step 1 is for mending for anode the material that lithium provides lithium source, comprise lithium powder, lithium powder slurry, lithium band, punching lithium band and rich lithium organic substance (as 1,4-butyl two lithium, 1,6-hexyl two lithium etc.) middle at least one.
One as the preparation method of lithium ion battery of the present invention is improved, rich lithium material described in step 1 is non-continuous state, and the single equivalent diameter d without lithium region of the rich lithium material of non-continuous state is (when equivalent aperture diameter refers to and hole area is converted into an area of a circle, described diameter of a circle) be no more than 4cm, two are no more than 4cm without the width a in lithium region that has between lithium region.
One as the preparation method of lithium ion battery of the present invention is improved, and complex method described in step 1 is treating the rich lithium material of the one side compound of rich lithium anode sheet or treating the rich lithium material of the two-sided compound of rich lithium anode sheet, and the face pressure of compound tense is 0.5MPa ~ 50MPa.
One as the preparation method of lithium ion battery of the present invention is improved, the object of cathode sheets process described in step 2 is in cathode sheets, form electrolyte diffusion admittance, acceleration electrolyte infiltrates, and concrete grammar comprises: laser treatment, corona treatment, mechanical treatment manufacture electrolyte transmission channel, ceramic coating, PVDF coating; The object of barrier film process described in step 2 is on barrier film, form electrolyte diffusion admittance, accelerates electrolyte and infiltrates, and concrete grammar comprises ceramic coating, PVDF coating; Described naked battery core assembling mode is lamination or winding.
One as the preparation method of lithium ion battery of the present invention is improved, and naked battery core described in step 3 enters shell for entering aluminum hull or entering box hat, and naked battery core enters bag for entering aluminum plastic film bag or entering rustless steel membrane bag; Described acceleration infiltration fluid injection mode clamps after battery core keeps liquid level not have naked battery core and fluid injection when comprising the steps: negative pressure liquid injection, fluid injection and extrudes battery core.
One as the preparation method of lithium ion battery of the present invention is improved, the fluid injection mode being convenient to electrolyte infiltration described in step 3 can also be: naked battery core step 2 obtained is soaked in electrolyte, thus accelerates electrolyte by naked battery core end to end to the diffusion at naked battery core center.
One as the preparation method of lithium ion battery of the present invention is improved, and the temperature of the control of solid electrolyte film described in step 4 (SEI film) film formation reaction is 20 DEG C ~ 70 DEG C; Time is 30min ~ 15h, and the face pressure of applying is 0.01MPa ~ 0.6MPa.
One as the preparation method of lithium ion battery of the present invention is improved, charging modes described in step 5 is for freely to charge or fixture is exerted pressure charging, charging current is that (C is battery capacity value to 0.01C ~ 5C, such as, if battery capacity is 1500mAh, then 1C is the electric current of 1500mA), charge capacity is 3% ~ 90%SOC (i.e. charged state, 10%SOC is the state during capacity of battery charging system 10%), temperature is 10 DEG C ~ 100 DEG C, and applying pressure is 0 ~ 4MPa.
When using the method to prepare lithium ion battery, because target and barrier film have carried out the process being conducive to electrolyte infiltration, therefore after fluid injection, prioritizing selection barrier film or cathode sheets spread to battery core zone line by electrolyte; Injection process have selected again the mode fluid injection be convenient to electrolyte and infiltrated simultaneously, therefore, it is possible to realize the infiltration to whole cathode sheets and barrier film with prestissimo, electrolyte diffuses to anode more afterwards, realizes the infiltration to whole battery core.Simultaneously, by the temperature left standstill after control injection process and fluid injection, the film forming speed of the first wetted area SEI film of effective control (reduction), be reduced to the consumption of film additive in electrolyte impregnation process, finally guarantee that the electrolyte component infiltrating each position of anode diaphragm (mainly battery core head-tail and battery core center) is consistent; Thus realize the good consistency of the SEI film that battery core electrode regional is formed.
Embodiment
Below in conjunction with embodiment, the present invention and beneficial effect thereof are described in detail, but embodiments of the present invention are not limited thereto.
Comparative example 1, the preparation of rich lithium electrode: select silicon-carbon compound to be anode active material, evenly obtain slurry with conductive agent, bonding agent and deionized water and stirring, be coated on copper current collector afterwards, cold pressing, itemize, welding, dry after rubberizing; Select metal lithium bands to be rich lithium source, use the face pressure of 5MPa, metal lithium bands is compounded in electrode two sides and obtains rich lithium electrode sheet.
The preparation of naked battery core: select cobalt acid lithium to be that cathode active material and conductive agent, bonding agent and n-formyl sarcolysine base Topiramate Los oxazolidinone stir and obtain slurry, be coated in afterwards on aluminium fluid, cold pressing, itemize, welding, dried for standby after rubberizing; Afterwards barrier film, cathode sheets, rich lithium anode sheet winding are obtained naked battery core.
Fluid injection leaves standstill: select aluminum plastic film to be that encapsulating material carries out top side seal, fluid injection encapsulation in 25 DEG C of environment afterwards, then leaves standstill 48h in 25 DEG C of environment, and electrolyte is fully infiltrated; In impregnation process, owing to there is electrical potential difference between lithium band and anode strip, when forming ion channel, lithium in lithium band is by spontaneous embedding silicon carbon material, the additive consumed in electrolyte is formed SEI film simultaneously, finally cause: along with electrolyte infiltrates to battery core center end to end from battery core, in electrolyte, additive level reduces phenomenon gradually.
Prepared by finished product battery core: in 35 DEG C of environment, and adopt 0.5C electric current to charge to above-mentioned battery core, charging capacity is 40%SOC, and the face pressure applied during charging is 1.0MPa; Finished product battery core is obtained afterwards through shaping, degasification.
Comparative example 2, with comparative example 1 unlike, this comparative example comprises the steps:
The preparation of rich lithium electrode: select silicon-carbon compound to be anode active material, evenly obtain slurry with conductive agent, bonding agent and deionized water and stirring, be coated on copper current collector afterwards, cold pressing, itemize, welding, dry after rubberizing; Select porous metals lithiums band be rich lithium source (equivalent aperture diameter and single be 0.2cm without lithium region equivalent diameter d, between holes, that is spacing two is 1cm without the lithium peak width a that has between lithium region), use the face pressure of 5MPa, metal lithium bands is compounded in electrode two sides and obtains rich lithium electrode sheet.
All the other are identical with comparative example 1, repeat no more.
Embodiment 1, with comparative example 1 unlike, the present embodiment comprises the steps:
The preparation of rich lithium electrode: with comparative example 1.
Naked battery core preparation: select cobalt acid lithium to be that cathode active material and conductive agent, bonding agent and n-formyl sarcolysine base Topiramate Los oxazolidinone stir and obtain slurry, be coated on aluminium fluid afterwards, cold pressing, itemize, corona equipment is adopted to process coating surface afterwards, make electrode surface more be conducive to electrolyte to infiltrate, then weld, rubberizing, dry after stand-by; Barrier film is carried out ceramic coating process, makes barrier film surface more be conducive to the infiltration of electrolyte; Again rich lithium anode sheet, cathode sheets and above-mentioned barrier film winding is obtained naked battery core.
Fluid injection leaves standstill: select aluminum plastic film to be that encapsulating material carries out top side seal, in 25 DEG C of environment, vacuum liquid filling is carried out to battery core afterwards, thus accelerate the wetting velocity accelerating battery core further, then 1h is left standstill in 45 DEG C of environment, make electrolyte fully infiltrate cathode sheets and barrier film; Because anode does not do special process, wetting velocity is comparatively slow, without ion channel between metal lithium bands and anode, embedding lithium film formation reaction can not occur.
Solid electrolyte film (SEI film) film formation reaction control: by leave standstill after battery core apply 0MPa face pressure, be placed in 45 DEG C of environment 20h, in the process, electrolyte will add to anode strip nearby and anode strip is fully infiltrated from cathode sheets and barrier film, lithium simultaneously in rich lithium material layer enters anode active material inside, and forms SEI film.
Prepared by finished product battery core: with comparative example 1.
All the other are identical with comparative example 1, repeat no more.
Embodiment 2, as different from Example 1, the present embodiment comprises the steps:
The preparation of rich lithium electrode: select silicon-carbon compound to be anode active material, evenly obtain slurry with conductive agent, bonding agent and deionized water and stirring, be coated on copper current collector afterwards, cold pressing, itemize, welding, dry after rubberizing; Select porous metals lithiums band be rich lithium source (equivalent aperture diameter and single be 0.2cm without lithium region equivalent diameter d, between holes, that is spacing two is 1cm without the lithium peak width a that has between lithium region), use the face pressure of 50MPa, metal lithium bands is compounded in electrode two sides and obtains rich lithium electrode sheet.
Naked battery core preparation: select cobalt acid lithium to be that cathode active material and conductive agent, bonding agent and n-formyl sarcolysine base Topiramate Los oxazolidinone stir and obtain slurry, be coated on aluminium fluid afterwards, cold pressing, itemize, laser equipment is adopted to process coating surface afterwards, apply one deck ceramic coating again, make electrode surface more be conducive to electrolyte to infiltrate, then weld, rubberizing, dry after stand-by; Barrier film is carried out ceramic coating, then at ceramic coating layer surface application one deck PVDF, makes barrier film surface more be conducive to the infiltration of electrolyte; Again rich lithium anode sheet, cathode sheets and above-mentioned barrier film winding is obtained naked battery core.
Fluid injection leaves standstill: select aluminum plastic film to be that encapsulating material carries out top side seal, in 80 DEG C of environment, vacuum liquid filling is carried out to battery core afterwards, vacuumize after again 0.6MPa air pressure 1min being applied to cavity, accelerate the wetting velocity of battery core in triplicate further, in 80 DEG C of environment, leave standstill 10min again, make electrolyte fully infiltrate cathode sheets and barrier film; Because anode does not do special process, wetting velocity is comparatively slow, without ion channel between metal lithium bands and anode, embedding lithium film formation reaction can not occur.
Solid electrolyte film (SEI film) film formation reaction control: by leave standstill after battery core apply 0.4MPa face pressure, be placed in 60 DEG C of environment 4h, in the process, hole through porous lithium sheet is added to anode strip nearby and anode strip is fully infiltrated by electrolyte from cathode sheets and barrier film, lithium simultaneously in rich lithium material layer enters anode active material inside, and forms SEI film.
Prepared by finished product battery core: with comparative example 1.
All the other are identical with embodiment 1, repeat no more.
Embodiment 3, the preparation of rich lithium electrode: select silicon-carbon compound to be anode active material, evenly obtain slurry with conductive agent, bonding agent and deionized water and stirring, be coated on copper current collector afterwards, cold pressing, itemize, welding, dry after rubberizing; Select porous metals lithiums band be rich lithium source (equivalent aperture diameter and single be 4cm without lithium region equivalent diameter d, between holes, that is spacing two is 4cm without the lithium peak width a that has between lithium region), use the face pressure of 0.5MPa, metal lithium bands is compounded in electrode two sides and obtains rich lithium electrode sheet.
Naked battery core preparation: select cobalt acid lithium to be that cathode active material and conductive agent, bonding agent and n-formyl sarcolysine base Topiramate Los oxazolidinone stir and obtain slurry, be coated on aluminium fluid afterwards, cold pressing, itemize, laser equipment is adopted to process coating surface afterwards, apply one deck ceramic coating again, make electrode surface more be conducive to electrolyte to infiltrate, then weld, rubberizing, dry after stand-by; Barrier film is carried out ceramic coating, then at ceramic coating layer surface application one deck PVDF, makes barrier film surface more be conducive to the infiltration of electrolyte; Again rich lithium anode sheet, cathode sheets and above-mentioned barrier film winding is obtained naked battery core.
Fluid injection leaves standstill: select aluminum plastic film to be that encapsulating material carries out top side seal, in 0 DEG C of environment, vacuum liquid filling is carried out to battery core afterwards, vacuumize after again 0.6MPa air pressure 1min being applied to cavity, in triplicate, again battery core is extruded after encapsulation, the wetting velocity of further quickening battery core, then 4h is left standstill in 0 DEG C of environment, make electrolyte fully infiltrate cathode sheets and barrier film; Because anode does not do special process, wetting velocity is comparatively slow, without ion channel between metal lithium bands and anode, embedding lithium film formation reaction can not occur.
Solid electrolyte film (SEI film) film formation reaction control: by leave standstill after battery core apply 4MPa face pressure, be placed in 95 DEG C of environment 10min, in the process, hole through porous lithium sheet is added to anode strip nearby and anode strip is fully infiltrated by electrolyte from cathode sheets and barrier film, lithium simultaneously in rich lithium material layer enters anode active material inside, and forms SEI film.
Prepared by finished product battery core: in 10 DEG C of environment, and adopt 0.01C electric current to charge to above-mentioned battery core, charging capacity is 20%SOC, and the face pressure applied during charging is 4MPa; Finished product battery core is obtained afterwards through shaping, degasification.
Embodiment 4, the preparation of rich lithium electrode: select silicon-carbon compound to be anode active material, evenly obtain slurry with conductive agent, bonding agent and deionized water and stirring, be coated on copper current collector afterwards, cold pressing, itemize, welding, dry after rubberizing; Select porous metals lithiums band be rich lithium source (equivalent aperture diameter and single be 0.1cm without lithium region equivalent diameter d, between holes, that is spacing two is 0.5cm without the lithium peak width a that has between lithium region), use the face pressure of 1MPa, metal lithium bands is compounded in electrode two sides and obtains rich lithium electrode sheet.
Naked battery core preparation: select cobalt acid lithium to be that cathode active material and conductive agent, bonding agent and n-formyl sarcolysine base Topiramate Los oxazolidinone stir and obtain slurry, be coated on aluminium fluid afterwards, cold pressing, itemize, laser equipment is adopted to process coating surface afterwards, apply one deck ceramic coating again, make electrode surface more be conducive to electrolyte to infiltrate, then weld, rubberizing, dry after stand-by; Barrier film is carried out ceramic coating, then at ceramic coating layer surface application one deck PVDF, makes barrier film surface more be conducive to the infiltration of electrolyte; Again rich lithium anode sheet, cathode sheets and above-mentioned barrier film winding is obtained naked battery core.
Fluid injection leaves standstill: above-mentioned naked battery core be soaked in 60 DEG C of electrolyte, vacuumize and adopt pressing mechanism to carry out extruding acceleration infiltration to naked battery core surface simultaneously, aluminum plastic film is selected to carry out top side seal as encapsulating material afterwards, in 80 DEG C of environment, leave standstill 1min again, make electrolyte fully infiltrate cathode sheets and barrier film; Because anode does not do special process, wetting velocity is comparatively slow, without ion channel between metal lithium bands and anode, embedding lithium film formation reaction can not occur.
Solid electrolyte film (SEI film) film formation reaction control: by leave standstill after battery core apply 0.6MPa face pressure, be placed in 70 DEG C of environment 1h, in the process, hole through porous lithium sheet is added to anode strip nearby and anode strip is fully infiltrated by electrolyte from cathode sheets and barrier film, lithium simultaneously in rich lithium material layer enters anode active material inside, and forms SEI film.
Prepared by finished product battery core: in 60 DEG C of environment, and adopt 1C electric current to charge to above-mentioned battery core, charging capacity is 70%SOC, and the face pressure applied during charging is 1MPa; Finished product battery core is obtained afterwards through shaping, degasification.
Embodiment 5, the preparation of rich lithium electrode: with embodiment 4.
Naked battery core preparation: with embodiment 4.
Fluid injection leaves standstill: select aluminum plastic film to be that encapsulating material carries out top side seal, in 35 DEG C of environment, vacuum liquid filling is carried out to battery core afterwards, vacuumize after again 0.6MPa air pressure 1min being applied to cavity, in triplicate, again battery core is extruded after encapsulation, the wetting velocity of further quickening battery core, then 2h is left standstill in 35 DEG C of environment, make electrolyte fully infiltrate cathode sheets and barrier film; Because anode does not do special process, wetting velocity is comparatively slow, without ion channel between metal lithium bands and anode, embedding lithium film formation reaction can not occur.
Solid electrolyte film (SEI film) film formation reaction control: by leave standstill after battery core apply 0.01MPa face pressure, be placed in 10 DEG C of environment 15h, in the process, hole through porous lithium sheet is added to anode strip nearby and anode strip is fully infiltrated by electrolyte from cathode sheets and barrier film, lithium simultaneously in rich lithium material layer enters anode active material inside, and forms SEI film.
Prepared by finished product battery core: in 100 DEG C of environment, and adopt 5C electric current to charge to above-mentioned battery core, charging capacity is 20%SOC, and the face pressure applied during charging is 1MPa; Finished product battery core is obtained afterwards through shaping, degasification.
Embodiment 6, the preparation of rich lithium electrode: select silicon-carbon compound to be anode active material, evenly obtain slurry with conductive agent, bonding agent and deionized water and stirring, be coated on copper current collector afterwards, cold pressing, itemize, welding, dry after rubberizing; Select porous metals lithiums band be rich lithium source (equivalent aperture diameter and single be 0.1cm without lithium region equivalent diameter d, between holes, that is spacing two is 0.5cm without the lithium peak width a that has between lithium region), use the face pressure of 10MPa, metal lithium bands is compounded in electrode two sides and obtains rich lithium electrode sheet.
Naked battery core preparation: select cobalt acid lithium to be that cathode active material and conductive agent, bonding agent and n-formyl sarcolysine base Topiramate Los oxazolidinone stir and obtain slurry, be coated on aluminium fluid afterwards, cold pressing, itemize, laser equipment is adopted to process coating surface afterwards, apply one deck ceramic coating again, make electrode surface more be conducive to electrolyte to infiltrate, then weld, rubberizing, dry after stand-by; Barrier film is carried out ceramic coating, then at ceramic coating layer surface application one deck PVDF, makes barrier film surface more be conducive to the infiltration of electrolyte; Again rich lithium anode sheet, cathode sheets and above-mentioned barrier film winding is obtained naked battery core.
Fluid injection leaves standstill: above-mentioned naked battery core be soaked in 60 DEG C of electrolyte, vacuumize and adopt pressing mechanism to carry out extruding acceleration infiltration to naked battery core surface simultaneously, aluminum plastic film is selected to carry out top side seal as encapsulating material afterwards, in 60 DEG C of environment, leave standstill 20min again, make electrolyte fully infiltrate cathode sheets and barrier film; Because anode does not do special process, wetting velocity is comparatively slow, without ion channel between metal lithium bands and anode, embedding lithium film formation reaction can not occur.
Solid electrolyte film (SEI film) film formation reaction control: by leave standstill after battery core apply 0.3MPa face pressure, be placed in 20 DEG C of environment 2h, in the process, hole through porous lithium sheet is added to anode strip nearby and anode strip is fully infiltrated by electrolyte from cathode sheets and barrier film, lithium simultaneously in rich lithium material layer enters anode active material inside, and forms SEI film.
Prepared by finished product battery core: in 70 DEG C of environment, and adopt 0.2C electric current to charge to above-mentioned battery core, charging capacity is 10%SOC, and the face pressure applied during charging is 0MPa; Finished product battery core is obtained afterwards through shaping, degasification.
Embodiment 7, the preparation of rich lithium electrode: selection graphite is anode active material, evenly obtains slurry with conductive agent, bonding agent and deionized water and stirring, is coated in afterwards on Porous Cu collector, colds pressing, itemize, welding, dry after rubberizing; Select porous metals lithiums band be rich lithium source (equivalent aperture diameter and single be 0.1cm without lithium region equivalent diameter d, between holes, that is spacing two is 0.5cm without the lithium peak width a that has between lithium region), use the face pressure of 10MPa, metal lithium bands is compounded in electrode one side and obtains rich lithium electrode sheet.
Naked battery core preparation: select LiFePO4 to be that cathode active material and conductive agent, bonding agent and n-formyl sarcolysine base Topiramate Los oxazolidinone stir and obtain slurry, be coated on porous aluminum fluid afterwards, cold pressing, itemize, laser equipment is adopted to process coating surface afterwards, apply one deck ceramic coating again, make electrode surface more be conducive to electrolyte to infiltrate, then weld, rubberizing, dry after stand-by; Barrier film is carried out ceramic coating, then at ceramic coating layer surface application one deck PVDF, makes barrier film surface more be conducive to the infiltration of electrolyte; Again rich lithium anode sheet, cathode sheets and above-mentioned barrier film winding is obtained naked battery core.
Fluid injection leaves standstill: above-mentioned naked battery core be soaked in 60 DEG C of electrolyte, vacuumize and adopt pressing mechanism to carry out extruding acceleration infiltration to naked battery core surface simultaneously, aluminum plastic film is selected to carry out top side seal as encapsulating material afterwards, in 60 DEG C of environment, leave standstill 20min again, make electrolyte fully infiltrate cathode sheets and barrier film; Because anode does not do special process, wetting velocity is comparatively slow, without ion channel between metal lithium bands and anode, embedding lithium film formation reaction can not occur.
Solid electrolyte film (SEI film) film formation reaction control: by leave standstill after battery core apply 0.3MPa face pressure, be placed in 20 DEG C of environment 2h, in the process, hole through porous lithium sheet is added to anode strip nearby and anode strip is fully infiltrated by electrolyte from cathode sheets and barrier film, lithium simultaneously in rich lithium material layer enters anode active material inside, and forms SEI film.
Prepared by finished product battery core: in 70 DEG C of environment, and adopt 0.2C electric current to charge to above-mentioned battery core, charging capacity is 3%SOC, and the face pressure applied during charging is 1.2MPa; Finished product battery core is obtained afterwards through shaping, degasification.
Embodiment 8, the preparation of rich lithium electrode: selection graphite is anode active material, evenly obtains slurry with conductive agent, bonding agent and deionized water and stirring, is coated in afterwards on Porous Cu collector, colds pressing, itemize, welding, dry after rubberizing; Select metallic lithium powder to be rich lithium source (lithium powder footpath is 50um), use the face pressure of 10MPa, metallic lithium powder is compounded in electrode one side and obtains rich lithium electrode sheet.
Naked battery core preparation: select sulphur carbon complex to be that cathode active material and conductive agent, bonding agent and n-formyl sarcolysine base Topiramate Los oxazolidinone stir and obtain slurry, be coated on porous aluminum fluid afterwards, cold pressing, itemize, welding, rubberizing, drying, more stand-by after adopting metal lithium bands to carry out rich lithium to this sulphur carbon cathode; Barrier film is carried out ceramic coating, then at ceramic coating layer surface application one deck PVDF, makes barrier film surface more be conducive to the infiltration of electrolyte; Again rich lithium anode sheet, cathode sheets and above-mentioned barrier film winding is obtained naked battery core.
Fluid injection leaves standstill: above-mentioned naked battery core be soaked in 60 DEG C of electrolyte, vacuumize and adopt pressing mechanism to carry out extruding acceleration infiltration to naked battery core surface simultaneously, aluminum plastic film is selected to carry out top side seal as encapsulating material afterwards, in 60 DEG C of environment, leave standstill 20min again, make electrolyte fully infiltrate cathode sheets and barrier film; Because anode does not do special process, wetting velocity is comparatively slow, without ion channel between metallic lithium powder and anode, embedding lithium film formation reaction can not occur.
Solid electrolyte film (SEI film) film formation reaction control: by leave standstill after battery core apply 0.3MPa face pressure, be placed in 60 DEG C of environment 30min, in the process, gap between lithium powder and lithium powder is added to anode strip nearby and anode strip is fully infiltrated by electrolyte from cathode sheets and barrier film, lithium simultaneously in rich lithium material layer enters anode active material inside, and forms SEI film.
Prepared by finished product battery core: in 70 DEG C of environment, and adopt 0.2C electric current to charge to above-mentioned battery core, charging capacity is 90%SOC, and the face pressure applied during charging is 0.8MPa; Finished product battery core is obtained afterwards through shaping, degasification.
Characterize and test:
Volume test: to the battery core in comparative example 1,2 and embodiment 1 ~ embodiment 7, respectively get 100, by following flow process, volume test is carried out to battery core in 35 DEG C of environment: leave standstill 3min; 0.5C constant current charge is to 4.2V, and constant voltage charge is to 0.05C; Leave standstill 3min; 0.5C constant-current discharge obtains discharge capacity D0 first to 3.0V; Complete volume test after leaving standstill 3min, calculate the mean value of the capacity of 100 battery cores in each group afterwards, and the Sigma of calculated capacity; Acquired results is in table 1.
Get battery core in 100 embodiments 8, in 35 DEG C of environment, by following flow process, volume test is carried out to battery core: leave standstill 3min; 0.5C constant current charge is to 2.8V, and constant voltage charge is to 0.05C; Leave standstill 3min; 0.5C constant-current discharge obtains discharge capacity D0 first to 1.5V; Complete volume test after leaving standstill 3min, calculate the mean value of the capacity of 100 battery cores in each group afterwards, and the Sigma of calculated capacity; Acquired results is in table 1.
Loop test: to the battery core in comparative example 1,2 and embodiment 1 ~ embodiment 7, respectively get 5, carry out loop test in 35 DEG C of environment, flow process is: leave standstill 3min; 0.5C constant current charge is to 4.2V, and constant voltage charge is to 0.05C; Leave standstill 3min; 0.5C constant-current discharge obtains discharge capacity first to 3.0V, and calculating the average size often organizing 5 battery cores is afterwards D
0; Leave standstill after 3min, the above-mentioned flow process of Posterior circle within 500 weeks, record battery core capacity, calculating the average size often organizing 5 battery cores is afterwards D
499, then battery core capability retention η=D
499/ D
0* 100%, acquired results is in table 1.
Get battery core in 5 embodiments 8, in 35 DEG C of environment, carry out loop test, flow process is: leave standstill 3min; 0.5C constant current charge is to 2.8V, and constant voltage charge is to 0.05C; Leave standstill 3min; 0.5C constant-current discharge obtains discharge capacity first to 1.5V, and calculating the average size often organizing 5 battery cores is afterwards D
0; Leave standstill after 3min, the above-mentioned flow process of Posterior circle within 500 weeks, record battery core capacity, calculating the average size often organizing 5 battery cores is afterwards D
499, then battery core capability retention η=D
499/ D
0* 100%, acquired results is in table 1.
According to table 1, comparative examples 1,2 and embodiment 1 ~ 6 can obtain, and when adopting method of the present invention to prepare lithium ion battery, the battery core obtained has higher capacity, and capacity distribution is more concentrated; In addition, the cycle performance of battery core prepared of the present invention is better.
Can be obtained by embodiment 7,8, the method is practical and graphite/LiFePO4 system and lithium-sulfur cell system also, illustrates that the method has universality.
Table 1, the electrical property table of lithium ion battery prepared by the method for comparative example and embodiment
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change above-mentioned execution mode and revise.Therefore, the present invention is not limited to above-mentioned embodiment, and any apparent improvement of every those skilled in the art done by basis of the present invention, replacement or modification all belong to protection scope of the present invention.In addition, although employ some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. a preparation method for lithium ion battery, is characterized in that, comprises the steps:
Step 1, the preparation of rich lithium anode: by the slurry coating containing anode active material in anode collector, obtains after oven dry treating rich lithium anode sheet, then will treat that rich lithium anode sheet and rich lithium material compound obtain rich lithium anode;
Step 2, is convenient to the preparation of naked battery core that electrolyte infiltrates: process the cathode sheets after drying, or use the barrier film after process, then rich lithium anode prepared by cathode sheets, barrier film and step 1 is assembled the naked battery core obtaining being convenient to electrolyte and infiltrate;
Step 3, uses the fluid injection mode fluid injection be convenient to electrolyte and infiltrated: after the naked battery core that step 2 is obtained is entered shell/bag, and carry out acceleration and infiltrate fluid injection, sealing obtains the battery core after fluid injection, leaves standstill 1min ~ 4h afterwards; Whole process control battery core temperature is 0 DEG C ~ 80 DEG C;
Step 4, the control of solid electrolyte film (SEI film) film formation reaction: to leave standstill after battery core apply 0 ~ 4MPa face pressure after, be placed in 10 DEG C ~ 95 DEG C environment 10min ~ 20h, make the lithium in rich lithium material layer enter anode active material inside, form SEI film simultaneously;
Step 5, the preparation of finished product battery core: battery core obtained for step 4 is carried out charge, shaping, degasification obtain finished product battery core.
2. a preparation method for lithium ion battery described in claim 1, is characterized in that, the anode active material described in step 1 comprises at least one in graphite, silicon, oxide and lithium titanate; Described collector is continuum fluid or porous current collector.
3. a preparation method for lithium ion battery described in claim 1, is characterized in that, the rich lithium material described in step 1, for mending for anode the material that lithium provides lithium source, comprises at least one in lithium powder, lithium powder slurry, lithium band, punching lithium band and rich lithium organic substance.
4. the preparation method of lithium ion battery described in a claim 1, it is characterized in that, rich lithium material described in step 1 is non-continuous state, and the single equivalent diameter d without lithium region of the rich lithium material of non-continuous state is no more than 4cm, two are no more than 4cm without the width a in lithium region that has between lithium region.
5. the preparation method of lithium ion battery described in a claim 1, it is characterized in that, complex method described in step 1 is treating the rich lithium material of the one side compound of rich lithium anode sheet or treating the rich lithium material of the two-sided compound of rich lithium anode sheet, and the face pressure of compound tense is 0.5MPa ~ 50MPa.
6. a preparation method for lithium ion battery described in claim 1, is characterized in that, the target sheet described in step 2 carries out that processing method is laser treatment, corona treatment, mechanical treatment to be to manufacture electrolyte transmission channel, ceramic coating or PVDF coating; The method of barrier film process described in step 2 is ceramic coating or PVDF coating.
7. a preparation method for lithium ion battery described in claim 1, is characterized in that, naked battery core described in step 3 enters shell for entering aluminum hull or entering box hat, and naked battery core enters bag for entering aluminum plastic film bag or entering rustless steel membrane bag; Described acceleration infiltration fluid injection mode clamps after battery core keeps liquid level not have naked battery core and fluid injection when comprising the steps: negative pressure liquid injection, fluid injection and extrudes battery core.
8. the preparation method of lithium ion battery described in a claim 1, it is characterized in that, the fluid injection mode being convenient to electrolyte infiltration described in step 3 can also be: naked battery core step 2 obtained is soaked in electrolyte, thus accelerates electrolyte by naked battery core end to end to the diffusion at naked battery core center.
9. a preparation method for lithium ion battery described in claim 1, is characterized in that, the temperature of the control of solid electrolyte film described in step 4 (SEI film) film formation reaction is 20 DEG C ~ 70 DEG C; Time is 30min ~ 15h, and the face pressure of applying is 0.01MPa ~ 0.6MPa.
10. a preparation method for lithium ion battery described in claim 1, is characterized in that, charging modes described in step 5 is for freely to charge or fixture is exerted pressure charging, charging current is 0.01C ~ 5C, charge capacity is 3% ~ 90%SOC, and temperature is 10 DEG C ~ 100 DEG C, and applying pressure is 0 ~ 4MPa.
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| CN111987362A (en) * | 2020-10-09 | 2020-11-24 | 昆山宝创新能源科技有限公司 | Lithium ion battery electrolyte and preparation method and application thereof |
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