CN104733783A - Preparation method of lithium ion battery - Google Patents
Preparation method of lithium ion battery Download PDFInfo
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- CN104733783A CN104733783A CN201510152253.5A CN201510152253A CN104733783A CN 104733783 A CN104733783 A CN 104733783A CN 201510152253 A CN201510152253 A CN 201510152253A CN 104733783 A CN104733783 A CN 104733783A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to the technical field of lithium ion batteries and particularly relates to a preparation method of a lithium ion battery. The preparation method comprises the steps of electrode preparation; lithium-enriched layer layout; injection formation (SEI film formation); lithium embedding in a lithium-enriched layer; finished product battery cell preparation and the like. When the lithium ion battery is prepared by using the method, a lithium-enriched substance layer is lightly compounded on the surface of an anode at the pressure of not higher than 0.5MPa during lithium enriching to ensure that the contact between the lithium-enriched substance layer and the surface of an electrode is reduced or avoided as much as possible, so that the condition that an SEI film with relatively poor structure and performance consistency is formed while lithium in the lithium-enriched substance layer soaked by electrolyte is embedded into an active substance of an anode is reduced or avoided, and furthermore, the prepared battery cell has more excellent electrochemical performance.
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
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, rich lithium layer is arranged, fluid injection changes into (forming SEI film), prepared by the embedding lithium of rich lithium layer, finished product battery core.The method is used to prepare lithium ion battery, when rich lithium, by rich lithium material layer gently (composite pressure is not more than 0.5MPa) be compound in anode surface, reduce as far as possible, avoid the contact of rich lithium material layer and electrode surface, thus reduce, avoid electrolyte to infiltrate after lithium in rich lithium material layer embed anode active material and form the poor SEI film of structural behaviour consistency simultaneously, the battery core therefore prepared has more excellent chemical property.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for lithium ion battery, comprises the steps:
Step 1, treats the preparation of rich lithium electrode: by the slurry coating containing anode active material on a current collector, colds pressing after drying and obtains treating rich lithium electrode;
Step 2, battery core preparation to be changed: rich lithium material is attached to gently step 1 the electrode obtained surface, the rich lithium material layer of one deck is formed at anode surface, described rich lithium material layer is the porous structure layer of rich lithium material composition, and this rich lithium material layer and anode active material surface form the least possible electron channel, the pressure used during attachment is 0 ~ 0.5MPa; Afterwards with dry after cathode sheets, barrier film be assembled into naked battery core, enter fluid injection after shell/bag, leave standstill;
Or be: step 2, battery core preparation to be changed: by step 1 gained anode, naked battery core is assembled into the cathode sheets (containing cathode active material) after oven dry, barrier film, in naked battery core assembling process, rich lithium material layer is arranged again between barrier film and anode strip, now can guarantee under less anode and rich lithium material layer bonding force, the exactitude position between two-layer; Afterwards naked battery core is entered fluid injection after shell/bag, leave standstill;
Step 3, solid electrolyte film (SEI film) generates: the battery core that the electrolyte obtained step 2 fully infiltrates changes into, changing into temperature is 10 DEG C ~ 90 DEG C, charging current is that (C is battery capacity value to 0.01 ~ 5C, such as, if battery capacity is 1500mAh, then 1C is the electric current of 1500mA), be 0 ~ 0.5MPa to battery core applied pressure when changing into, charging SOC (i.e. charged state, 10%SOC is the state during capacity of battery charging system 10%) is 3% ~ 90%;
Step 4, embedding lithium: to the face pressure of battery core applying 0.5MPa ~ 5.0MPa that step 3 obtains, anode surface after making rich lithium material layer and forming SEI film fully contacts (formation electron channel), owing to there is electrical potential difference between rich lithium material layer and anode, lithium in rich lithium material layer embeds in spontaneous anode active material layer, and final realization mends lithium effect;
Step 5, finished product battery core makes: the battery core that step 4 is obtained carries out shaping, degasification obtains finished product battery core.
One as the preparation method of lithium ion battery of the present invention is improved, and anode strip described in step 1 is made up of the anodic coating containing anode active material and anode collector; Cathode sheets described in step 2 is made up of the cathode containing cathode active material and collector; Described cathode is or/and anodic coating is for lacking lithium layer; Concrete, described anode active material comprises material with carbon element (graphite, disordered carbon), carbon compound (B ~ C ~ N series, C ~ Si ~ O series), non-carbon material (metal oxide, lithium ~ transition metal nitride, lithium alloy); Described cathode active material comprises at least one in lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, oxide/lithium ferrite, lithium-barium oxide, ternary or multiple elements design compound, sulphur or sulfide/sulfur compound cathode material and polyanion cathode material.
One as the preparation method of lithium ion battery of the present invention is improved, rich lithium material described in step 2 is for mending for anode the material that lithium provides lithium source, comprise lithium powder, lithium powder slurry, lithium band, punching lithium band, 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, the equivalent aperture diameter of the porous structure layer of rich lithium material composition described in step 2 (when equivalent aperture diameter refers to and hole area is converted into an area of a circle, described diameter of a circle) is no more than 4cm; Continuous rich lithium layer width (pitch of holes) between holes is no more than 4cm.
One as the preparation method of lithium ion battery of the present invention is improved, and described in step 2, the equivalent aperture diameter of the porous structure layer of rich lithium material composition is preferably more than 2cm; Continuous rich lithium layer width (pitch of holes) between holes is preferably more than 2cm.
One as the preparation method of lithium ion battery of the present invention is improved, and the pressure used when step 2 is adhered to is preferably 0 ~ 0.1MPa.
One as the preparation method of lithium ion battery of the present invention is improved, and adhering mode described in step 2 is treating the one side attachment of rich lithium anode or treating the two-sided attachment of rich lithium anode.
One as the preparation method of lithium ion battery of the present invention is improved, and battery core assembling mode described in step 2 is for winding is or/and lamination; It is aluminum hull or box hat that naked battery core enters shell, and it is aluminum plastic film or rustless steel membrane that naked battery core enters bag; Described fluid injection mode is common fluid injection or vacuum liquid filling; Described dwell temperature is 10 DEG C ~ 100 DEG C, and the time is 1min ~ 72h.
One as the preparation method of lithium ion battery of the present invention is improved, and change into temperature described in step 3 and be preferably 35 DEG C ~ 85 DEG C, charging current is preferably 0.01 ~ 1C, is preferably 0 ~ 0.1MPa when changing into battery core applied pressure, and charging SOC is 3% ~ 60%.
One as the preparation method of lithium ion battery of the present invention is improved, and apply face pressure to battery core described in step 4 and be preferably 0.5MPa ~ 2.0MPa, temperature is 20 DEG C ~ 100 DEG C, and the time is 10min ~ 48h.
The method is used to prepare lithium ion battery, can effectively slow down/suppress in electrolyte impregnation process, lithium anode active material particle inside embedding in rich lithium material layer, reduces/eliminates the generation (because this type of embedding lithium process directly contacted is uncontrollable process) of the SEI film of anode interior structural behaviour consistency difference; Meanwhile, change into flow process by controlled charging, form structure and the homogeneous SEI film of property infiltrating sufficient anode active material surface; Fill after point process formed until SEI film by controlled, again pressure is applied to battery core, rich lithium material layer is fully contacted with between anode active material, formation electronics leads to, under the driving of the electrical potential difference again between anode and rich lithium material layer, the lithium in rich lithium material layer is derived from thinking of sending out and embeds between anode active material; Finally obtain the rich lithium ion battery that capacity is high, cycle performance is more excellent.
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 the naked battery core of rich lithium: 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, dried for standby after rubberizing; 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; With metal lithium bands be rich lithium source, according to full battery first efficiency be 95% capacity relationship select lithium band, adopt the face pressure of 2MPa by lithium band compound anode surface after the drying afterwards; Above-mentioned cathode sheets, rich lithium anode sheet winding are obtained naked battery core.
The formation of SEI film: above-mentioned naked battery core is packaged in aluminum plastic film the battery core obtained after closedtop; According to relationship between quality, the selection LiPF of EC:DEC:PC:VC:FEC=35:35:30:1:5 (VC, FEC are additive)
6for lithium salts configuration electrolyte is for subsequent use; Above-mentioned electrolyte is injected the battery core Vacuum Package after above-mentioned closedtop; In 35 DEG C of environment, place 24h makes electrolyte fully infiltrate; Along with the infiltration of electrolyte in process, there is voltage difference between the rich lithium material adhered to due to anode surface and anode active material, will automatically impel the generation of anode active material particle surface SEI;
Prepared by finished product battery core: above-mentioned obtained battery core is carried out shaping, degasification obtains finished product battery core.
Comparative example 2, the preparation of the naked battery core of rich lithium: 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, dried for standby after rubberizing; 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; With porous metals lithium band, for rich lithium source, (hole shape is circular, bore dia is 0.4cm, pitch of holes is 1cm), according to full battery first efficiency be 95% capacity relationship select lithium band, adopt the face pressure of 2MPa by lithium band compound anode surface after the drying afterwards; Above-mentioned cathode sheets, rich lithium anode sheet winding are obtained naked battery core.
The formation of SEI film: above-mentioned naked battery core is packaged in aluminum plastic film the battery core obtained after closedtop; According to relationship between quality, the selection LiPF of EC:DEC:PC:VC:FEC=35:35:30:1:5 (VC, FEC are additive)
6for lithium salts configuration electrolyte is for subsequent use; Above-mentioned electrolyte is injected the battery core Vacuum Package after above-mentioned closedtop; In 35 DEG C of environment, place 24h makes electrolyte fully infiltrate; Along with the infiltration of electrolyte in process, there is voltage difference between the rich lithium material adhered to due to anode surface and anode active material, will automatically impel the generation of anode active material particle surface SEI;
Prepared by finished product battery core: above-mentioned obtained battery core is carried out shaping, degasification obtains finished product battery core.
Embodiment 1, treat 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 in afterwards on continuous print copper current collector, cold pressing, itemize, welding, dried for standby after rubberizing;
Battery core to be changed 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 in afterwards on aluminium fluid, cold pressing, itemize, welding, dried for standby after rubberizing; By above-mentioned gained anode, naked battery core is wound into cathode sheets, barrier film, in naked battery core assembling process, arrange again between barrier film and anode strip rich lithium material layer (with metal lithium bands be rich lithium source, according to full battery first efficiency be 95% capacity relationship select lithium tape thickness), now be equivalent to not apply pressure bonding between lithium band and anode strip, pass through the exactitude position of the control realization negative electrode of winding process, anode, barrier film and lithium band simultaneously; Select aluminum plastic film to be that exterior packaging material carries out encapsulating afterwards, fluid injection, to leave standstill.
SEI film generates: by sufficient for above-mentioned infiltration battery core, change at 45 DEG C, applying pressure is 0MPa, and charging current is 0.05C, and charging SOC is 30%, makes anode surface form SEI film.
Embedding lithium: to the battery core of above-mentioned formation SEI film, apply the face pressure of 1.0MPa, be positioned over again in 45 DEG C of environment and leave standstill 12h, make to form electron channel closely between lithium band and anode strip, under electrical potential difference effect now between lithium band and anode, lithium metal carries out benefit lithium by automatically embedding antianode in anode strip.
Finished product battery core makes: above-mentioned obtained battery core is carried out shaping, degasification obtains finished product battery core.
Embodiment 2, as different from Example 1, the present embodiment comprises the steps:
Treat the preparation of rich lithium electrode: with embodiment 1.
Battery core to be changed 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 in afterwards on aluminium fluid, cold pressing, itemize, welding, dried for standby after rubberizing; Select porous lithium band to be rich lithium source, hole shape is circular, and bore dia is 0.4cm, and pitch of holes is 1cm, and porous lithium band is compounded in anode strip overlay both sides and obtains lithium anode combination electrode by the 0.05MPa face pressure of use, then is wound into naked battery core with cathode sheets, barrier film; Select aluminum plastic film to be that exterior packaging material carries out encapsulating afterwards, fluid injection, to leave standstill.
SEI film generates: by sufficient for above-mentioned infiltration battery core, change at 70 DEG C, applying pressure is 0.05MPa, and charging current is 0.2C, and charging SOC is 40%, makes anode surface form SEI film.
Embedding lithium: to the battery core of above-mentioned formation SEI film, apply the face pressure of 0.8MPa, be positioned over again in 60 DEG C of environment and leave standstill 8h, make to form electron channel closely between lithium band and anode strip, under electrical potential difference effect now between lithium band and anode, lithium metal carries out benefit lithium by automatically embedding antianode in anode strip.
All the other are identical with embodiment 1, repeat no more.
Embodiment 3, as different from Example 2, the present embodiment comprises the steps:
Treat the preparation of rich lithium electrode: with embodiment 1.
Battery core to be changed 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 in afterwards on aluminium fluid, cold pressing, itemize, welding, dried for standby after rubberizing; Select porous lithium band to be rich lithium source, hole shape is circular, and bore dia is 4cm, and pitch of holes is 4cm, and porous lithium band is compounded in anode strip overlay both sides and obtains lithium anode combination electrode by the 0.5MPa face pressure of use, then is wound into naked battery core with cathode sheets, barrier film; Select aluminum plastic film to be that exterior packaging material carries out encapsulating afterwards, fluid injection, to leave standstill.
SEI film generates: by sufficient for above-mentioned infiltration battery core, change at 90 DEG C, applying pressure is 0.5MPa, and charging current is 5C, and charging SOC is 60%, makes anode surface form SEI film.
Embedding lithium: to the battery core of above-mentioned formation SEI film, apply the face pressure of 5MPa, be positioned over again in 100 DEG C of environment and leave standstill 1h, make to form electron channel closely between lithium band and anode strip, under electrical potential difference effect now between lithium band and anode, lithium metal carries out benefit lithium by automatically embedding antianode in anode strip.
All the other are identical with embodiment 2, repeat no more.
Embodiment 4, as different from Example 2, the present embodiment comprises the steps:
Treat the preparation of rich lithium electrode: with embodiment 1.
Battery core to be changed 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 in afterwards on aluminium fluid, cold pressing, itemize, welding, dried for standby after rubberizing; Select porous lithium band to be rich lithium source, hole shape is circular, and bore dia is 2cm, and pitch of holes is 2cm, and porous lithium band is compounded in anode strip overlay both sides and obtains lithium anode combination electrode by the 0.1MPa face pressure of use, then is wound into naked battery core with cathode sheets, barrier film; Select aluminum plastic film to be that exterior packaging material carries out encapsulating afterwards, fluid injection, to leave standstill.
SEI film generates: by sufficient for above-mentioned infiltration battery core, change at 85 DEG C, applying pressure is 0.1MPa, and charging current is 1C, and charging SOC is 50%, makes anode surface form SEI film.
Embedding lithium: to the battery core of above-mentioned formation SEI film, apply the face pressure of 2MPa, be positioned over again in 70 DEG C of environment and leave standstill 4h, make to form electron channel closely between lithium band and anode strip, under electrical potential difference effect now between lithium band and anode, lithium metal carries out benefit lithium by automatically embedding antianode in anode strip.
All the other are identical with embodiment 2, repeat no more.
Embodiment 5, as different from Example 2, the present embodiment comprises the steps:
Treat the preparation of rich lithium electrode: with embodiment 1.
Battery core to be changed 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 in afterwards on aluminium fluid, cold pressing, itemize, welding, dried for standby after rubberizing; Porous lithium band is selected to be rich lithium source, hole shape is square, and equivalent aperture diameter is 0.9cm, and pitch of holes is 1.6cm, porous lithium band is compounded in anode strip overlay both sides and obtains lithium anode combination electrode by the 0.07MPa face pressure of use, then is wound into naked battery core with cathode sheets, barrier film; Select aluminum plastic film to be that exterior packaging material carries out encapsulating afterwards, fluid injection, to leave standstill.
SEI film generates: by sufficient for above-mentioned infiltration battery core, change at 70 DEG C, applying pressure is 0.07MPa, and charging current is 0.5C, and charging SOC is 40%, makes anode surface form SEI film.
Embedding lithium: to the battery core of above-mentioned formation SEI film, apply the face pressure of 1MPa, be positioned over again in 20 DEG C of environment and leave standstill 48h, make to form electron channel closely between lithium band and anode strip, under electrical potential difference effect now between lithium band and anode, lithium metal carries out benefit lithium by automatically embedding antianode in anode strip.
All the other are identical with embodiment 2, repeat no more.
Embodiment 6, as different from Example 2, the present embodiment comprises the steps:
Treat the preparation of rich lithium electrode: with embodiment 1.
Battery core to be changed 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 in afterwards on aluminium fluid, cold pressing, itemize, welding, dried for standby after rubberizing; Porous lithium band is selected to be rich lithium source, hole shape is triangle, and equivalent aperture diameter is 0.1cm, and pitch of holes is 0.5cm, porous lithium band is compounded in anode strip overlay both sides and obtains lithium anode combination electrode by the 0.02MPa face pressure of use, then is wound into naked battery core with cathode sheets, barrier film; Select aluminum plastic film to be that exterior packaging material carries out encapsulating afterwards, fluid injection, to leave standstill.
SEI film generates: by sufficient for above-mentioned infiltration battery core, change at 10 DEG C, applying pressure is 0.04MPa, and charging current is 0.01C, and charging SOC is 40%, makes anode surface form SEI film.
Embedding lithium: to the battery core of above-mentioned formation SEI film, apply the face pressure of 0.5MPa, be positioned over again in 40 DEG C of environment and leave standstill 24h, make to form electron channel closely between lithium band and anode strip, under electrical potential difference effect now between lithium band and anode, lithium metal carries out benefit lithium by automatically embedding antianode in anode strip.
All the other are identical with embodiment 2, repeat no more.
Embodiment 7, as different from Example 2, the present embodiment comprises the steps:
Treat 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, be coated on the copper current collector of porous afterwards, cold pressing, itemize, welding, dried for standby after rubberizing.
Battery core to be changed 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 in afterwards on aluminium fluid, cold pressing, itemize, welding, dried for standby after rubberizing; Select porous lithium band to be rich lithium source, hole shape is circular, and bore dia is 0.4cm, and pitch of holes is 1cm, and anode strip overlay is one-sided obtains lithium anode combination electrode to use 0.05MPa face pressure to be compounded in by porous lithium band, then is wound into naked battery core with cathode sheets, barrier film; Select aluminum plastic film to be that exterior packaging material carries out encapsulating afterwards, fluid injection, to leave standstill.
SEI film generates: by sufficient for above-mentioned infiltration battery core, change at 70 DEG C, applying pressure is 0.05MPa, and charging current is 0.2C, and charging SOC is 90%, makes anode surface form SEI film.
Embedding lithium: to the battery core of above-mentioned formation SEI film, apply the face pressure of 0.8MPa, be positioned over again in 60 DEG C of environment and leave standstill 8h, make to form electron channel closely between lithium band and anode strip, under electrical potential difference effect now between lithium band and anode, lithium metal carries out benefit lithium by automatically embedding antianode in anode strip.
All the other are identical with embodiment 2, repeat no more.
Embodiment 8, as different from Example 2, the present embodiment comprises the steps:
Treat 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, be coated on the copper current collector of porous afterwards, cold pressing, itemize, welding, dried for standby after rubberizing.
Battery core to be changed 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 aluminium fluid afterwards, cold pressing, itemize, welding, rubberizing, the rich lithium technology of lithium band is adopted to carry out rich lithium to the sulphur negative electrode obtained, stand-by afterwards; Select metallic lithium powder to be rich lithium source, lithium powder footpath is 50um; Anode strip overlay is one-sided obtains lithium anode combination electrode to use 0.05MPa face pressure to be compounded in by lithium powder, then becomes naked battery core with cathode sheets, barrier film lamination; Select aluminum plastic film to be that exterior packaging material carries out encapsulating afterwards, fluid injection, to leave standstill.
SEI film generates: by sufficient for above-mentioned infiltration battery core, change at 70 DEG C, applying pressure is 0.05MPa, and charging current is 0.2C, and charging SOC is 90%, makes anode surface form SEI film.
Embedding lithium: to the battery core of above-mentioned formation SEI film, apply the face pressure of 0.8MPa, be positioned over again in 60 DEG C of environment and leave standstill 8h, make to form electron channel closely between lithium powder and anode strip, under electrical potential difference effect now between lithium powder and anode, lithium metal carries out benefit lithium by automatically embedding antianode in anode strip.
All the other are identical with embodiment 2, repeat no more.
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.
Table 1, the electrical property table of lithium ion battery prepared by the method for comparative example and embodiment
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.
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, treats the preparation of rich lithium anode: by the slurry coating containing anode active material in anode collector, colds pressing after drying and obtains treating rich lithium anode;
Step 2, battery core preparation to be changed: the surface for the treatment of rich lithium anode rich lithium material being attached to step 1 gained, to treat that rich lithium anode surface forms the rich lithium material layer of one deck, obtain rich lithium anode, described rich lithium material layer is the porous structure layer be made up of rich lithium material, and this rich lithium material layer is attached to anode active material surface, the pressure used during attachment is 0 ~ 0.5MPa; Afterwards rich lithium anode and the cathode sheets after drying, barrier film are assembled into naked battery core, after entering shell/bag, inject electrolyte, leave standstill;
Or be: step 2, the preparation of battery core to be changed: by step 1 gained until rich lithium anode with dry after cathode sheets, barrier film be assembled into naked battery core, in the assembling process of naked battery core, at barrier film and treat to arrange rich lithium material layer between rich lithium anode; Afterwards naked battery core is entered fluid injection after shell/bag, leave standstill;
Step 3, the generation of SEI film: change into the battery core fully infiltrated through electrolyte that step 2 obtains, changing into temperature is 10 DEG C ~ 90 DEG C, and charging current is 0.01 ~ 5C, be 0 ~ 0.5MPa to battery core applied pressure when changing into, charging SOC is 3% ~ 90%;
Step 4, embedding lithium: to the face pressure of battery core applying 0.5MPa ~ 5.0MPa that step 3 obtains, anode surface after making rich lithium material layer and forming SEI film fully contacts, to form electron channel, owing to there is electrical potential difference between rich lithium material layer and anode, lithium in rich lithium material layer embeds in spontaneous anode active material layer, and final realization mends lithium effect;
Step 5, the making of finished product battery core: the battery core that step 4 is obtained carries out shaping, degasification obtains finished product battery core.
2. a preparation method for lithium ion battery according to claim 1, is characterized in that, the cathode sheets described in step 2 is made up of the cathode containing cathode active material and collector; Described anode active material comprises at least one in material with carbon element, carbon compound and non-carbon material; Described cathode active material comprises at least one in lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, oxide/lithium ferrite, lithium-barium oxide, ternary or multiple elements design compound, sulphur or sulfide/sulfur compound cathode material and polyanion cathode material.
3. the preparation method of a lithium ion battery according to claim 1, it is characterized in that, rich lithium material described in step 2, 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. a preparation method for lithium ion battery according to claim 1, is characterized in that, the equivalent aperture diameter of the porous structure layer be made up of rich lithium material described in step 2 is no more than 4cm; Continuous rich lithium layer width between holes is no more than 4cm.
5. a preparation method for lithium ion battery according to claim 4, is characterized in that, the equivalent aperture diameter of the porous structure layer be made up of rich lithium material described in step 2 is for being no more than 2cm; Continuous rich lithium layer width between holes is no more than 2cm.
6. a preparation method for lithium ion battery according to claim 1, is characterized in that, the pressure used when adhering in step 2 is 0 ~ 0.1MPa.
7. a preparation method for lithium ion battery according to claim 1, is characterized in that, adhering mode described in step 2 is treating the one side attachment of rich lithium anode or treating the two-sided attachment of rich lithium anode.
8. a preparation method for lithium ion battery according to claim 1, is characterized in that, in step 2, naked battery core 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 fluid injection mode is normal pressure fluid injection or vacuum liquid filling; Described standing temperature is 10 DEG C ~ 100 DEG C, and leaving standstill the time continued is 1min ~ 72h.
9. a preparation method for lithium ion battery according to claim 1, is characterized in that, the temperature that changes into described in step 3 is 35 DEG C ~ 85 DEG C, and charging current is 0.01 ~ 1C, is 0 ~ 0.1MPa to battery core applied pressure when changing into, and charging SOC is 3% ~ 60%.
10. a preparation method for lithium ion battery according to claim 1, is characterized in that, the face pressure applied battery core described in step 4 is 0.5MPa ~ 2.0MPa, and temperature is 20 DEG C ~ 100 DEG C, and the time is 10min ~ 48h.
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