CN104953186B - The preparation technology and negative pole of a kind of lithium ion battery mend lithium device - Google Patents
The preparation technology and negative pole of a kind of lithium ion battery mend lithium device Download PDFInfo
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- CN104953186B CN104953186B CN201510420680.7A CN201510420680A CN104953186B CN 104953186 B CN104953186 B CN 104953186B CN 201510420680 A CN201510420680 A CN 201510420680A CN 104953186 B CN104953186 B CN 104953186B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
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Abstract
Lithium device, preparation technology are mended the invention provides a kind of preparation technology of lithium ion battery and negative pole：Under inert atmosphere protection, negative plate is melted into as working electrode using lithium device is mended to negative plate；The negative plate being melted into is taken out from lithium device is mended again, by drying process, positive plate, barrier film and negative plate are then assembled into electrode group, the electrode group and electrolyte are encapsulated in battery container, complete battery is obtained.Described benefit lithium device include upper and lower substrate, insulation board (2), collector (3), lug (4), working electrode (7), barrier film (8), to electrode (9), sealing ring (6).The technique and device can reduce electrode material waste, improve the performance of the batteries such as battery energy density.
Description
Technical field
Lithium device is mended the present invention relates to the preparation technology and negative pole of lithium ion battery, more particularly to a kind of lithium ion battery.
Background technology
Lithium ion battery has high voltage, high-energy-density, long circulation life and security performance compared to other secondary cells
The advantage such as good, as most widely used rechargeable battery, has captured portable type electronic product power supply market at present, and gradually
Electrokinetic cell is elected as by the Large-scale Mobile equipment such as electric automobile, however, the performance of dynamic lithium battery is also far from meeting people's
Demand.On the other hand, portable wearable device is pursued by people, but high performance flexible battery required for it is limitation
Its key factor developed.No matter lithium ion battery is as electrokinetic cell or flexible battery, and cost has to be reduced, energy
Density and power density all need further raising.
The development work of novel anode material is like a raging fire, but the production of lithium ion battery is basic and the first two does not have for 10 years
Much difference, still do negative material, novel anode material is difficult to be commercially used popularization, and reason has varied using graphite,
But initial coulomb efficiency is relatively low and preceding circulate several times unstable is very important factor.And preparation technology limitation ripe at present
The popularization and the raising of lithium ion battery combination property of new negative electrode materials for lithium secondary batteries.
Because positive electrode capacity will be far below capacity of negative plates, current conventional lithium ion battery design is upper general using " lithium ion
The mode of total amount limitation ", i.e., typically use limited positive pole, and uses excessive negative pole, the lithium ion so come out from positive pole
Negative pole will not be made to reach embedding lithium saturation state (formation that otherwise there will be metal Li dendrite, cause security incident).Negative pole is first
Efficiency for charge-discharge is extremely important be exactly because in the battery system of above-mentioned " mode of lithium ion total amount limitation ", lithium ion it is total
Amount, available quantity just determine the capacity of lithium ion battery.Best negative pole is exactly that how many lithium ion obtained from positive pole when charging, and is put
Just return positive pole how many lithium ion when electric, but actual conditions be battery during first charge-discharge, negative pole can consume a part
Lithium ion from positive pole forms larger irreversible capacity, so most to form SEI films and participate in some irreversible reactions
The lithium ion of positive pole can be returned to eventually to be reduced, and the actual capacity of battery will be reduced.Therefore battery irreversible capacity causes electricity
Pole waste of material, coulombic efficiency reduction causes the reduction of the performances such as the energy content of battery and power density.At present to how to eliminate battery not
The harmful effect that reversible capacity is caused also is applied without good mode in production.
In terms of energy and power density is improved, according to its calculation formula it is known that in the constant feelings of energy and power
It is one of effective method to reduce battery weight under condition, and it is pith to reduce battery electrode material quality, and leaf flies (leaf
Fly the special-shaped polymer lithium ion battery preparation techniques of and improve research [D] Beijing of energy density：The National University of Defense technology,
2008：62.) by with the LiCoO of industrial comparative maturity2The lithium ion battery of negative pole is used as positive pole, business BTR carbon materials
Negative pole surplus capacity is reduced to 17%, encapsulating film proportion by 17% by 33% and is reduced to the energy density of battery after 1l% by 110Wh/kg liters
For 131Wh/ks.Research is it has also been found that a material facts more than：Negative pole surplus capacity reaches in common lithium ion battery
33%,
In terms of energy and power density is improved, it is fundamental way to improve electrode material performance, has there is substantial amounts of at present
New electrode materials are produced, although it is that its capacity and high rate performance are improved that most electrode materials, which are suffered from a problem that,
, but it is first or the preceding coulombic efficiency circulated several times is relatively low, is accomplished by additionally adding some electrodes in actual assembled battery
Material supplements the irreversible capacity caused by coulombic efficiency is low, so will result in the waste of a large amount of electrode materials, on the contrary can
Increase battery cost and the reduction energy content of battery and power density.Therefore benefit lithium is carried out to electrode to be particularly important.Currently in order to
Reduce the reduction for the battery capacity that the irreversible capacity due to battery during first charge-discharge is brought, existing some patents text
Offer and report some solutions.It is different with mode according to principle, physics can be divided into and mend lithium and electrochemistry benefit lithium.Physics mends lithium
Substantially thinking is exactly to be mixed by lithium powder by different modes or with negative material, or be covered in negative material surface even bear
Pole surface, to realize the supplement that excessive lithium is consumed to negative pole.Representative have Japan Patent JP1996027910 and
JP2005038720, Chinese patent application CN1290209C, CN201310094757.7, CN1830110A and
CN201210351225.2.But added lithium metal after electrolyte by these methods, reaction speed is quickly；Lithium is mended in negative pole
When, the SEI films resulted in are unstable, while negative material is easily broken, in addition, remaining in some lithium metals of electrode surface
Particle and the accessory substance of lithium metal reaction can form Li dendrite, pierce through barrier film and cause cell safety hidden danger.
Form the method for SEI films on the surface of negative pole in advance to supplement irreversible capacity first by charge and discharge cycles, then
The method for being assembled into battery with positive plate progress, referred to as electrochemistry mend lithium.Patent application CN200710195790.3 and
CN2010107458.9 proposes the thinking of pre-formed SEI films, but the thinking of pre-formed SEI films can greatly improve capacity first
The specific discharge capacity of reversible rate and battery, can improve cycle performance of battery and will not form Li dendrite in negative pole again.But this
A little patent document method therefors or just for graphite cathode, although or statement be directed to non-Carbon anode, the method used for
The type negative materials such as hard charcoal, nano-carbon material, silicon alloy and silicon/carbon composite are clearly inapplicable, because absolutely mostly
Not only efficiency is low, it is necessary to can be only achieved stable state through repeatedly circulation first for number material.Do not have in this kind of patent document simultaneously
The special purpose device of effect, introduces method or excessively coarse or cost is too high, is unfavorable for promoting.
We mend lithium thinking using electrochemistry, according to the operation principle of actual lithium battery, develop one kind and are more suitable for reality
The lithium ion battery preparation technology of application, is provided in particular in the benefit lithium device of specialty, and benefit lithium is carried out to negative pole, improves the storehouse of negative pole
Human relations efficiency, eliminates first or the preceding harmful effect that causes of circulation irreversible capacity several times, improves the coulombic efficiency of whole battery, subtract
Few electrode material is wasted, and improves the energy density and power density of battery, while preferably promoting the business of high-performance negative material
Industry popularization and application.
The content of the invention
Lithium device, the technique and dress are mended it is an object of the invention to provide a kind of preparation technology of lithium ion battery and negative pole
Electrode material waste can be reduced by putting, and improve the battery performances such as battery energy density, and then promote the business of high-performance negative material
Change popularization and application.
To reach above-mentioned purpose, the present invention starts with from the formation mechenism of lithium ion battery charge and discharge process and SEI films, will be negative
Pole piece to electrode, barrier film and electrolyte with, using lithium device is mended, under inert atmosphere protection, being assembled into simulated battery, to the mould
Intend battery to be melted into；Then under inert gas shielding, the negative plate being melted into is taken out from lithium device is mended, will
Positive, negative electrode plate is assembled into electrode group with barrier film, and the electrode group and electrolyte are encapsulated in battery container.This method and device
It can be used for assembling battery, the coulombic efficiency of the battery electrode piece of assembling is higher and cycle performance is preferable, can eliminate lithium-ion electric
Electrode irreversible capacity influences in pond, so as to realize that reduction electrode material wastes, improves battery energy density.
The present invention is using technical scheme in detail below：
A kind of preparation technology of lithium ion battery, step includes：
1) under inert atmosphere protection, negative plate is melted into as working electrode using lithium device is mended to negative plate；
2) under inert gas shielding, the negative plate being melted into is taken out from lithium device is mended, by drying process,
Then positive plate, barrier film and negative plate are assembled into electrode group, the electrode group and electrolyte is encapsulated in battery container, obtained
Complete battery；
Described benefit lithium device, including upper substrate, infrabasal plate, upper and lower substrate are connected with axle；Upper and lower substrate is embedded with absolutely
In listrium, insulation board cutting and by collector laying wherein, collector is closely connected with extraneous by lug；The lug of infrabasal plate
Positive pole is connect, the lug of upper substrate connects negative pole；Working electrode is close in infrabasal plate on collector, infiltrates a small amount of on working electrode
After electrolyte, barrier film is spread on the working electrode (s；Electrode is placed on the collector of upper substrate；Outside substrate edge, insulation board
Provided with seal groove, sealing ring is placed in seal groove；Upper and lower substrate can closely be snapped together by secure component.
The step 1) in negative plate be：It is made up of the negative material of collector and coating or filling on a current collector
Negative plate, or flexible negative plate.
Described negative material contains negative electrode active material, conductive agent and adhesive.Described negative electrode active material is selected from
Elementary silicon, silicon compound, silicon-carbon compound, silicon alloy, silicon metal composite, tin simple substance, tin compound, tin carbon complex, gold
Belong to the one or more in oxide, coke, graphene, CNT, nano-carbon material, porous carbon materials.
Described flexible negative plate is：Charcoal cloth, graphene film, carbon nano-tube film, flexible graphite paper, or have negative electrode active
Material adulterates or compound flexible negative plate.
The step 2) in the positive electrode that uses of positive plate for cobalt acid lithium, LiMn2O4, cobalt lithium nickel manganese oxide, LiFePO4
Any of lithium-containing compound is several.
The step 1) in negative plate be melted into condition be：0- is first discharged to using lithium device is mended as simulated battery
0.2V, is recharged to 0.5-3V, repeated multiple times until stable circulation；The electric current of the discharge process is in the range of 0.001-0.5C
A steady state value, the charging process electric current be 0.01-1C in the range of a steady state value.
A kind of negative electrode of lithium ion battery mends lithium device, including upper substrate, infrabasal plate, and upper and lower substrate is connected with axle；It is upper and lower
Substrate be embedded with insulation board, insulation board cutting and by collector laying wherein, collector is closely connected with extraneous by lug；
The lug of infrabasal plate connects positive pole, and the lug of upper substrate connects negative pole；Working electrode is close in infrabasal plate on collector, work electricity
After the extremely upper a small amount of electrolyte of infiltration, barrier film is spread on the working electrode (s；Electrode is placed on the collector of upper substrate；On infrabasal plate side
Edge, insulation board is externally provided with seal groove, seal groove and places sealing ring；Upper and lower substrate can closely be fastened by secure component
Together, it is to avoid outside moisture and air enter internal.
Described substrate can be the existing machinable material such as various metal materials, carbon material, high molecule plastic or resin
It is made；
Described insulation board is various insulating materials, such as polyvinyl fluoride plate, igelite etc.；
Described collector is film-form conductive material, such as common copper foil or aluminium foil；
Described lug is common wire such as copper cash, aluminum steel or other wires, and lug is closely connected with collector；
Described axle is various axles conventional in machine, instrument or part design, for connecting upper and lower substrate；
Described sealing ring can be rubber ring, Graphite pad or other can play the material of sealing function；
Described barrier film is porous film material prepared by the macromolecules such as polystyrene or polystyrene, it is allowed to which lithium ion passes through
Without allowing electronics to pass through；
Described is lithium paper tinsel or lithium alloy to electrode, or there is lithium paper tinsel of clad etc. on surface；
The form of described secure component can have a variety of, can be that flange form, button or screw-nut etc. can be played
The part of fastening effect.
Compared with prior art the invention has the advantages that, the present invention can be according to the electrode material of experimental determination
The basic data such as design such as coulombic efficiency, reversible capacity and cycle performance and assembled battery, it is special using what is provided in the present invention
Mend lithium device, by carrying out the technique that is melted into-assembles again to negative plate, preceding Loop partitioning several times opened, will before following several times
The lithium ion of ring consumption is provided electrode by lithium piece etc., and the electrode in actual battery has been that stable circulation, coulombic efficiency exist
More than 98% electrode, can so eliminate the harmful effect that electrode irreversible capacity is brought in lithium ion battery, realize and reduce
Electrode material wastes and improved the purpose of the performances such as battery energy density.Meanwhile, the present invention is based on above-mentioned technical process and special
Device can the low negative material of coulombic efficiency first and preceding coulombic efficiency several times is low or unstable but specific capacity be higher, circulate
The good negative material of performance is promoted the use of.
Brief description of the drawings
Fig. 1 is repeatable using lithium device (a) is mended for side-opening figure, and (b) is side-closure figure, and (c) bows for infrabasal plate
View.In figure：1-2 is that upper substrate, 1-1 are infrabasal plates, and 2 be insulation board, and 3 be collector, and 4 be lug, and 5 be axle, and 6 be sealing
Circle, 7 be working electrode, and 8 be barrier film, and 9 be that, to electrode, 10 be secure component.
Fig. 2 test schematic diagrams
A kind of silicon-carbon compounds of Fig. 3 as negative material cycle performance
A kind of Co of Fig. 43O4- C compounds as negative material cycle performance
A kind of SnO2-CNT compounds of Fig. 5 as negative material cycle performance
A kind of Fe of Fig. 63O4- GF compounds as negative material cycle performance
Embodiment
To make those skilled in the art more fully understand technical scheme, with reference to embodiment and accompanying drawing pair
The present invention is described in detail.
In benefit lithium device shown in Fig. 1, figure：(a) it is the benefit lithium device schematic front view of open mode, (b) is closed form
The benefit lithium device schematic front view of state, (c) is infrabasal plate schematic top plan view.Upper and lower substrate is circle, including 10 kinds of main portions
Part, the 26S Proteasome Structure and Function relation of each part is as follows：All parts are on upper and lower substrate, and upper and lower substrate is connected by axle 5, and
(Fig. 1 b) can be closely buckled together, wherein sealing ring 6 plays sealing function, secure component 10 can be by this device preferably
It is encapsulated, it is to avoid outside moisture and air, which enter, to be mended inside lithium device；Upper and lower substrate is embedded with insulation board 2, insulation board 2
Cutting simultaneously lays collector 3 wherein, and collector 3 is connected with the external world by lug 4, and infrabasal plate 1-1 corresponding is positive pole, upper base
Plate 1-2 corresponding is negative pole；Working electrode 7 is close in infrabasal plate 1-1 on collector 3, a small amount of electrolysis drop is drawn
On working electrode 7, after infiltration, barrier film 8 is layered on working electrode 7；Electrode is placed on upper substrate 1-2 collector 3,
All parts can close this device after being in place, fastening.
Embodiment 1
By using LiFePO4 be positive active material traditionally prepare positive pole, using silicon-carbon compound as negative electrode active
The negative plate that material is traditionally prepared respectively together with lithium piece (to electrode), electrolyte, barrier film, is used as working electrode
Repeatable utilize mends lithium device (see Fig. 1), under argon gas atmosphere protection, as illustrated places each composition one by one, is assembled into
Simulated battery, is melted into the simulated battery：Simulated battery is discharged to 0.01V with 0.01C current density, then will be put
Simulated battery after electricity charges to 2V with 0.05C current density, repeated multiple times until stable circulation；Then protected in argon gas
Under shield, the negative plate being melted into is taken out from lithium device is mended, by drying process, by the positive plate calculated and processing
The negative plate crossed is matched and is assembled into electrode group with barrier film by measure, and the electrode group and electrolyte are encapsulated in into battery container
It is interior, obtain completed cell.
Understood using simulated battery is (as shown in Figure 2) to negative material progress electro-chemical test, according to test result (as schemed
Shown in 3) carbon-silicon compound is as 7 circulation volumes before during negative material in reduction, and coulombic efficiency gradually increases, subsequent
In circulation, stabilization is always maintained at.In the present embodiment, the specific capacity of LiFePO4 is 140mAh/g, and monolithic negative pole contains 1g work
Property material, it can be seen from simulated battery experimental result, if directly with not carrying out chemical conversion treatment by the method provided of the invention
Electrode slice carry out battery assembling, it is necessary to LiFePO4 quality be 15.32g, the consumption of early stage irreversible capacity could be met,
And if the method provided using our invention, after first 7 times circulate, the electrode slice assembled battery by stable circulation,
Then only need to positive electrode 6.36g, it can be seen that have substantial amounts of, even more than actually the positive electrode for the amount of playing a role is wasted
.And the method provided using the present invention is pre-processed after negative material, it is only necessary to which calculating positive electrode consumption by stationary value can
So that all positive electrodes are all used for reversible circulation.The waste of positive electrode, the various property of battery will so be greatly reduced
It will also can be largely increased.
Embodiment 2
By the positive pole traditionally prepared using ferro-cobalt lithium as positive active material, with three cobalt oxides-carbon Co3O4- C is combined
Thing be the negative plate that traditionally prepares of negative electrode active material as working electrode respectively with lithium piece (to electrode), electrolyte,
Barrier film together, using repeatable using lithium device (accompanying drawing 1) is mended, under argon gas atmosphere protection, is constituted each one by one as illustrated
Place, be assembled into simulated battery, the simulated battery is melted into：Simulated battery is discharged to 0.1C current density
0V, then charges to 3V by the simulated battery after electric discharge with 0.5C current density, repeated multiple times until stable circulation；Then exist
Under argon gas protection, the electrode slice being melted into is taken out from lithium device is mended, by drying process, will be calculated just
Pole piece and treated negative electrode plate are matched and are assembled into electrode group with barrier film by measure, by the electrode group and electrolysis fluid-tight
In battery container, completed cell is obtained.
Understood using simulated battery is (as shown in Figure 2) to negative material progress electro-chemical test, according to test result (as schemed
Shown in 4) Co3O4- C compounds are as 4 circulation volumes before during negative material in reduction, and coulombic efficiency gradually increases, subsequent
Circulation in, be always maintained at stabilization.In the present embodiment, the specific capacity of cobalt acid lithium is 160mAh/g, and monolithic negative pole contains 1g work
Property material, it can be seen from simulated battery experimental result, if directly with not carrying out chemical conversion treatment by the method provided of the invention
Electrode slice carry out battery assembling, it is necessary to cobalt acid lithium quality be 8.44g, the consumption of early stage irreversible capacity could be met, and
If the method provided using our invention, after the first 4 times circulate, the electrode slice assembled battery by stable circulation, then
Only need to positive electrode 5g, it can be seen that there is substantial amounts of positive electrode to be wasted.And the method provided using the present invention is located in advance
Manage after negative material, it is only necessary to which calculating positive electrode consumption by stationary value just can be so that all positive electrodes are all used for reversible
Circulation.The waste of positive electrode will so be greatly reduced, the various performances of battery will also be largely increased.
Embodiment 3
By using ternary material be positive active material traditionally prepare positive pole, using SnO2-CNT compounds as negative pole
The negative plate that active material is traditionally prepared as working electrode respectively together with lithium piece (to electrode), electrolyte, barrier film,
Using repeatable using lithium device (accompanying drawing 1) is mended, under argon gas atmosphere protection, each composition is placed one by one as illustrated, group
Simulated battery is dressed up, the simulated battery is melted into：Simulated battery is discharged to 0V with 0.5C current density, then will be put
Simulated battery after electricity charges to 1V with 1C current density, repeated multiple times until stable circulation；Then protected in argon gas
Under, the electrode slice being melted into is taken out from lithium device is mended, by drying process, by the positive plate calculated and treated
Negative electrode plate matched by measure and be assembled into electrode group with barrier film, the electrode group and electrolyte are encapsulated in battery container
It is interior, obtain completed cell.
Understood using simulated battery is (as shown in Figure 2) to negative material progress electro-chemical test, according to test result (as schemed
Shown in 5) the SnO2-CNT compounds are as 14 circulation volumes before during negative material in reduction, and coulombic efficiency gradually increases,
In subsequent circulation, stabilization is always maintained at.In the present embodiment, the specific capacity of ternary material is 150mAh/g, and monolithic negative pole contains
1g active material, it can be seen from simulated battery experimental result, if be directly melted into the method not provided by the present invention
The electrode slice of processing carries out the assembling of battery, it is necessary to the quality of ternary material is 17.03g, could meet early stage irreversible capacity
Consumption, and if the method provided using our invention, after first 14 times circulate, the electrode slice group by stable circulation
Packed battery, then only need to positive electrode 5.47g, it can be seen that has substantial amounts of, is even more than the positive pole material of the actually amount of playing a role
Material is wasted.And the method provided using the present invention is pre-processed after negative material, it is only necessary to calculate positive electrode by stationary value
Consumption just can be so that all positive electrodes are all used for reversible circulation.The waste of positive electrode, battery will so be greatly reduced
Various performances will also be largely increased.
Embodiment 4
By the positive pole traditionally prepared using LiMn2O4 as positive active material, with Fe3O4- GF iron oxide-graphene film
Compound be the negative plate that traditionally prepares of negative electrode active material as working electrode respectively with lithium piece (to electrode), electrolysis
Liquid, barrier film together, using repeatable using lithium device (accompanying drawing 1) is mended, under argon gas atmosphere protection, constitute one by each as illustrated
One is placed, and is assembled into simulated battery, and the simulated battery is melted into：Simulated battery is discharged to 0.5C current density
0V, then charges to 1V by the simulated battery after electric discharge with 1C current density, repeated multiple times until stable circulation；Then in argon
Under gas gas shield, the electrode slice being melted into is taken out from lithium device is mended, by drying process, by the positive pole calculated
Piece and treated negative electrode plate are matched and are assembled into electrode group with barrier film by measure, and the electrode group and electrolyte are encapsulated
In battery container, completed cell is obtained.
Understood using simulated battery is (as shown in Figure 2) to negative material progress electro-chemical test, according to test result (as schemed
Shown in 6) Fe3O4- GF compounds gradually rise as 30 circulation volume earthquakes before during negative material, early stage reduction later stage,
Coulombic efficiency gradually increases, in subsequent circulation, is always maintained at stabilization.In the present embodiment, the specific capacity of LiMn2O4 is
150mAh/g, monolithic negative pole contains 1g active material, it can be seen from simulated battery experimental result, if directly with not by this hair
The electrode slice that the method for bright offer carries out chemical conversion treatment carries out the assembling of battery, it is necessary to which the quality of ternary material is 13.13g,
The consumption of early stage irreversible capacity can be met, and if the method provided using our invention, will after first 30 times circulate
The electrode slice assembled battery of stable circulation, then only need to positive electrode 8g, it can be seen that have substantial amounts of positive electrode to be wasted
.And the method provided using the present invention is pre-processed after negative material, it is only necessary to which calculating positive electrode consumption by stationary value can
So that all positive electrodes are all used for reversible circulation.The waste of positive electrode, the various property of battery will so be greatly reduced
It will also can be largely increased.
If in fact, not using the present invention, battery producer also will not carry out battery battery core using above-mentioned negative material
Prepare, first reason is exactly to waste too many positive electrode, although the capacity of above-mentioned negative material is higher by one times than graphite
More than, and if using the present invention, above mentioned problem there will be no, above-mentioned negative material will be promoted.
Claims (9)
1. a kind of preparation technology of lithium ion battery, it is characterised in that step includes：
1) under inert atmosphere protection, negative plate is melted into as working electrode using lithium device is mended to negative plate；Chemical conversion
Condition be：0-0.2V is first discharged to using lithium device is mended as simulated battery, 0.5-3V is recharged to, it is repeated multiple times until circulation
It is stable；The electric current of the discharge process is a steady state value in the range of 0.001-0.5C, and the charging process electric current is 0.01-
A steady state value in the range of 1C；
2) under inert gas shielding, the negative plate being melted into is taken out from lithium device is mended, by drying process, then
Positive plate, barrier film and negative plate are assembled into electrode group, the electrode group and electrolyte are encapsulated in battery container, obtains complete
Battery；
Described benefit lithium device, including upper substrate (1-2), infrabasal plate (1-1), upper and lower substrate are connected with axle (5)；Upper and lower substrate
Insulation board (2) is embedded with, insulation board (2) interior cutting simultaneously lays collector (3) wherein, and collector (3) passes through lug with the external world
(4) close connection；The lug of infrabasal plate connects positive pole, and the lug of upper substrate connects negative pole；Working electrode (7) is close to infrabasal plate (1-
1) on collector (3), working electrode is infiltrated after a small amount of electrolyte on (7), and barrier film (8) is layered on working electrode (7)；To electricity
Pole (9) is placed on upper substrate (1-2) collector (3)；At infrabasal plate (1-1) edge, insulation board (2) is externally provided with seal groove, close
Sealing ring (6) is placed in sealing groove；Upper and lower substrate can closely be snapped together by secure component (10).
2. a kind of preparation technology of lithium ion battery as claimed in claim 1, it is characterised in that the step 1) in negative pole
Piece is：The negative plate being made up of the negative material of collector and coating or filling on a current collector, or flexible negative plate.
3. a kind of preparation technology of lithium ion battery as claimed in claim 2, it is characterised in that described negative material contains
Negative electrode active material, conductive agent and adhesive.
4. a kind of preparation technology of lithium ion battery as claimed in claim 3, it is characterised in that described negative electrode active material
It is combined selected from elementary silicon, silicon compound, silicon-carbon compound, silicon alloy, silicon metal composite, tin simple substance, tin compound, tin carbon
One or more in thing, metal oxide, coke, graphene, CNT, nano-carbon material, porous carbon materials.
5. a kind of preparation technology of lithium ion battery as claimed in claim 2, it is characterised in that described flexible negative plate
For：Charcoal cloth, graphene film, carbon nano-tube film, flexible graphite paper, or there is negative electrode active material to adulterate or compound flexible negative pole
Piece.
6. a kind of preparation technology of lithium ion battery as claimed in claim 1, it is characterised in that the step 2) in positive pole
The positive electrode that piece is used is any of cobalt acid lithium, LiMn2O4, cobalt lithium nickel manganese oxide, LiFePO4 lithium-containing compound or several
Kind.
7. a kind of negative electrode of lithium ion battery mends lithium device, it is characterised in that upper and lower including upper substrate (1-2), infrabasal plate (1-1)
Substrate is connected with axle (5)；Upper and lower substrate is embedded with insulation board (2), and collector (3) is simultaneously laid it by insulation board (2) interior cutting
In, collector (3) is closely connected with the external world by lug (4)；The lug of infrabasal plate connects positive pole, and the lug of upper substrate connects negative pole；
Working electrode (7) is close in infrabasal plate (1-1) on collector (3), and working electrode is infiltrated after a small amount of electrolyte on (7), every
Film (8) is layered on working electrode (7)；Electrode (9) is placed on upper substrate (1-2) collector (3)；On infrabasal plate (1-1) side
Edge, insulation board (2), which is externally provided with seal groove, seal groove, places sealing ring (6)；Can be by upper and lower substrate by secure component (10)
Closely snap together.
8. a kind of negative electrode of lithium ion battery as claimed in claim 7 mends lithium device, it is characterised in that described collector (3)
For copper foil or aluminium foil；Described lug (4) is copper cash, aluminum steel or other wires.
9. a kind of negative electrode of lithium ion battery as claimed in claim 7 mends lithium device, it is characterised in that described sealing ring (6)
It is rubber ring or Graphite pad；Described is lithium paper tinsel or lithium alloy to electrode (9), or there is the lithium paper tinsel of clad on surface.
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| CN105702943B (en) * | 2016-01-30 | 2018-10-19 | 山西大学 | A kind of lithium ion battery negative material benefit lithium method |
| CN105810883A (en) * | 2016-05-24 | 2016-07-27 | 广州市霆宇能源科技有限责任公司 | Flexible wearable electrode and preparation method therefor |
| CN106450481B (en) * | 2016-12-07 | 2019-06-04 | 清华大学深圳研究生院 | A kind of lithium ion battery and preparation method thereof |
| CN106450488B (en) * | 2016-12-16 | 2019-09-03 | 天津力神电池股份有限公司 | A kind of in-situ preparation method of the lithium-sulfur cell based on silicium cathode |
| CN108155347B (en) * | 2017-12-06 | 2020-08-28 | 天津力神电池股份有限公司 | Method for improving first coulomb efficiency of nickel-containing anode material of lithium ion battery and application thereof |
| CN109638341A (en) * | 2018-11-23 | 2019-04-16 | 浙江衡远新能源科技有限公司 | A kind of lithium ion full battery and preparation method thereof |
| CN109755474A (en) * | 2018-12-29 | 2019-05-14 | 三明学院 | A kind of the benefit lithium method and benefit lithium device of lithium ion battery negative material |
| CN112034020A (en) * | 2020-08-19 | 2020-12-04 | 国联汽车动力电池研究院有限责任公司 | Method and device for measuring lithium pre-intercalation amount of negative electrode of lithium ion battery |
| CN114583179B (en) * | 2022-03-04 | 2024-04-26 | 远景动力技术(江苏)有限公司 | Flexible lithium ion battery and manufacturing method thereof |
| CN114975978A (en) * | 2022-06-24 | 2022-08-30 | 中山烯利来设备科技有限公司 | Method and device for supplementing lithium to outside of silicon material |
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| CN104200999B (en) * | 2014-08-26 | 2017-03-08 | 中国科学院电工研究所 | A kind of lithium-ion energy storage device |
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