CN109786841A - A kind of preparation method of lithium ion electrochemical energy storage device - Google Patents
A kind of preparation method of lithium ion electrochemical energy storage device Download PDFInfo
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- CN109786841A CN109786841A CN201811526450.9A CN201811526450A CN109786841A CN 109786841 A CN109786841 A CN 109786841A CN 201811526450 A CN201811526450 A CN 201811526450A CN 109786841 A CN109786841 A CN 109786841A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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
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Abstract
The present invention relates to energy storage device technical fields, more particularly to a kind of preparation method of lithium ion electrochemical energy storage device, it include: to be shorted the cathode of battery core and metal lithium electrode, and setting separates the diaphragm of the two between battery core and metal lithium electrode, by battery core, metal lithium electrode and diaphragm are packaged in shell, pre-buried at least one first pipe in the housing, after shell is sealed, enclosure interior is vacuumized, and inject electrolyte, blocking first pipe is connected to second pipe, the positive external power supply anode of battery core, the cathode external power supply cathode of battery core, after carrying out the pre- embedding lithium of charge and discharge electric treatment to the cathode of battery core, connection anode and cathode charge and discharge, seal the opening of the first pipe other end, and disconnect the connection of second pipe and first pipe, obtain lithium ion electrochemical energy storage device.The present invention provides one kind can be produced in non-protective atmosphere, the preparation method of pre- short, of good performance lithium ion electrochemical energy storage device of embedding lithium time.
Description
Technical field
The present invention relates to lithium ion electrochemical energy storage device technical fields, and in particular to a kind of lithium ion electrochemical accumulator
The preparation method of part.
Background technique
Country's energy resource system is increasingly turned to take electric power as leading new energy resources system by traditional fossil energy at present, is real
This existing target, energy storage device also develop to the direction of higher energy density, lower manufacturing cost, and wherein lithium ion electrochemical stores up
Can device due to its high-multiplying power discharge and cycle life more, become one of most promising direction.But current lithium ion electrification
The large-scale production for learning energy storage device there is also some problems, such as inevitably be related to the benefit lithium of cathode, rich solution system electricity
Solve removal etc. of gas during liquid removal, chemical conversion or high pressure-temperature, these operations are required in isolation moisture and oxygen
It is carried out in protective gas environment, it is difficult to it is compatible with existing production equipment, therefore production efficiency is lower.
In order to improve the energy density of above-mentioned lithium ion electrochemical energy storage device, needing to carry out it pre- embedding lithium or mend lithium behaviour
Make.But the bottleneck of i.e. pre- embedding lithium technique is that pre- embedding lithium overlong time, energy storage device performance are to be improved at present.Such as China
Patent document CN101310350A discloses a kind of pre-embedding lithium method, is to be stacked anode, partition, cathode, in portion, top layer
Divide and partition is respectively set on lowest level part, fixed four sides with adhesive tape, and passes through ultrasonic bonding for positive electrode collector
The terminal welding portion of terminal welding portion and negative electrode collector is welded on aluminium positive terminal and copper negative terminal, is obtained
Polar stack unit；One lithium electrode is respectively set in the upper and lower part of polar stack unit again, by resistance welding method by lithium
The terminal welding portion of electrode current collector is welded on negative terminal portion.After injecting electrolyte, sealing, after placing 20 days, metal
Lithium is just totally consumed, in addition inside electrical storage device there are unfavorable factors such as ohmic polarization, activation polarization and concentration polarizations, because
This causes pre- embedding lithium overlong time, while battery performance is also to be improved.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that overcoming lithium ion electrochemical energy storage device in the prior art raw
It produces and needs to carry out in the protective gas environment of exclusion of water and oxygen, production efficiency is lower, and pre- embedding lithium time length, lithium ion
The performance of electrochemical energy storing device defect to be improved, so that providing one kind can be given birth in non-protective atmosphere
It produces, and other equipment good compatibility, and production efficiency is higher, the pre- embedding lithium time is short, lithium ion electrochemical energy storage device performance
The preparation method of good lithium ion electrochemical energy storage device.
In order to solve the above-mentioned technical problems, the present invention provides a kind of preparation method of lithium ion electrochemical energy storage device,
Include:
The cathode of battery core and metal lithium electrode are shorted, and setting separates the two between the battery core and metal lithium electrode
Diaphragm, the battery core, metal lithium electrode and diaphragm are packaged in shell；The cathode is by negative current collector and is arranged on
Negative electrode active at layering form, the negative electrode active is at layering with a thickness of 20-90 microns；The anode of the battery core is by anode
Collector and the positive-active being arranged on are formed at layering, and the positive-active is at 20-180 microns of thickness of layering；
Pre-buried at least one first pipe, one end of the first pipe are placed in the enclosure interior in the shell,
The other end extends the shell and is connected to second pipe, and the shell is sealed；
The enclosure interior is vacuumized by the second pipe, electrolyte is injected, blocks the first pipe and institute
The connection for stating second pipe carries out pre- embedding lithium by cathode of the electrochemical method to the battery core；
After the anode is connected to progress charge and discharge with the cathode, it is connected to the first pipe and second pipe again
Road is evacuated, and the opening of the first pipe other end is sealed, and disconnects the company of the second pipe Yu the first pipe
It connects, obtains lithium ion electrochemical energy storage device；
The method of the pre- embedding lithium are as follows:
By the positive external power supply anode of the battery core, the cathode external power supply cathode of the battery core, after once charging
Primary electric discharge is carried out as a circulation or shelved after once charging as a circulation or be filled with constant current
Constant voltage charging is carried out after electricity as a circulation, and charge and discharge electric treatment is carried out to the cathode of the battery core, completes the battery core
The pre- embedding lithium of cathode；
The quality of lithium metal is m in the metal lithium electrode, and m meets following formula:
M=3.6* (A*Q)/(F*Z), wherein the unit of m is g, and A is metallic lithium atoms amount, unit g/mol, F farad
Constant, Z=1, Q are pre- embedding lithium capacity, and value is the 10-90% of capacity of negative plates, and the unit of Q is mAh.
The percent opening of the preparation method, the copper foil with through hole and the nickel foil with through hole is 2%-
30%, the percent opening of the aluminium foil with through hole is 2-30%.
The preparation method, the number of the circulation are 1-500 times.
The preparation method, the charge and discharge electric treatment are to charge to upper limit voltage with the electric current of 0.01-0.5C, shelve 1-
24h；
Alternatively, the charge and discharge electric treatment is with the electric current of 0.01-0.5C to charge to upper limit voltage, then with upper limit voltage constant pressure
Charge 1-24h；
Alternatively, the charge and discharge electric treatment is with the electric current of 0.01-0.5C to charge to upper limit voltage, then with upper limit voltage constant pressure
Charge 0.1-1h, then with the current discharge of 0.01-0.5C to blanking voltage, so repeats 1-10 times；
Alternatively, the charge and discharge electric treatment is with the electric current of 1-30C to charge to upper limit voltage, then with the current discharge of 1-30C
To blanking voltage, 1-10min is shelved, is so repeated 10-500 times.
The preparation method, the upper limit voltage are 3.8-4.2V；Upper limit voltage refers to the blanking voltage of charging；It is described
Blanking voltage is 2.0-2.5V, preferably 2.0V.
The preparation method, the pre- lithium-inserting amount of the cathode of the battery core are the 10-90%, preferably 75- of capacity of negative plates
85%；Here, cathode is about in the electrolytic solution 3.0V relative to the open circuit potential of metal lithium electrode, and capacity of negative plates is referred to gold
Belong to lithium electrode to be used as to electrode, cathode is put with the current density (quality based on negative electrode active ingredient) of 25mA/g from open circuit potential
Electricity to 0.01V discharge capacity.
The preparation method, the negative electrode active at the negative electrode active ingredient in layering be graphite, carbonaceous mesophase spherules,
At least one of hard carbon, soft carbon, the sub- silicon of oxidation, nanocrystal silicon；
The positive-active is nickle cobalt lithium manganate, nickel cobalt lithium aluminate, cobalt acid lithium, phosphoric acid at the positive-active ingredient in layering
At least one of iron lithium, porous carbon materials；Preferably, the porous carbon materials are in active carbon, carbon aerogels or graphene
At least one；The nickle cobalt lithium manganate is also referred to as tertiary cathode material, can use chemical formula LiNixCoyMnzO2It indicates, by transition
Metallic element composition difference can be divided into: LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、
LiNi0.7Co0.2Mn0.1O2、LiNi0.8Co0.1Mn0.1O2, NCM111, NCM523, NCM622, NCM721 and NCM811 can be used respectively
It indicates.The above material is commercially available material.
The preparation method, the metal lithium electrode is by metal lithium electrode collector and the metallic lithium foil group being arranged on
At.
The preparation method, the negative current collector are the copper foil with through hole or the nickel foil with through hole；
The plus plate current-collecting body is the aluminium foil with through hole.
The metal lithium electrode collector is with through hole copper foil, has through hole nickel foil, copper mesh, nickel screen, foam gold
Belong to copper or foam metal nickel, preferably there is through hole copper foil or copper mesh.
The preparation method, the battery core are formed after being stacked gradually or wound by cathode, diaphragm, anode, diaphragm；Such as
Lamination does the structure of battery core: diaphragm/cathode/diaphragm/anode/diaphragm/cathode/diaphragm；Winding does the structure of battery core: diaphragm/negative
Pole/diaphragm/anode；
The battery core at least two in the shell, the metal lithium electrode is between adjacent battery core.
The preparation method, the electrolyte are described to be containing lithium electrolyte salt by forming containing lithium electrolyte salt and solvent
Lithium hexafluoro phosphate, lithium perchlorate, LiBF4, double-fluoroform sulfimide lithium, at least one in double fluorine sulfimide lithiums
Kind, the solvent be propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, in vinylene carbonate at least
It is a kind of；The injection rate of the electrolyte be it is appropriate, be subject to and sufficiently infiltrate battery core.Electrolytic salt, solvent, lithium-ion electrolyte with
And diaphragm is commercially available.
In addition, positive (anode electrode piece) and cathode (negative electricity pole piece) the preparation method is as follows:
Anode is that the slurry comprising positive-active ingredient, conductive agent and binder is applied to containing 2-30% percent opening
On aluminium foil with through hole；Cathode is that the slurry comprising negative electrode active ingredient, conductive agent and binder is applied to containing 2-
On the copper foil or nickel foil with through hole of 30% percent opening.The percent opening refers to the area and collector in hole on collector
The ratio of area；
The binder be Kynoar (PVDF), polytetrafluoroethylene (PTFE) (PTFE), sodium carboxymethylcellulose (CMC),
Butadiene-styrene rubber (SBR) or Chengdu mattress ground at least one of happy LA series aqueous binders produced etc.；The conductive agent is selected from
At least one of conductive black, electrically conductive graphite or carbon nanotube.
The preparation method, the metallic lithium foil with a thickness of 0.9-1.5mm.
In addition, the meaning of C, according to " QB/T 2502-2000 lithium-ions battery generic specification ", C indicates that battery is put with 5h rate
Capacity when electricity to final voltage, in other words, 1C indicate that the current value of 1 times of capacity, 5C indicate the current value of 5 times of capacity.
Since lithium metal is a kind of very active element, potential differs greatly metal lithium electrode in the electrolytic solution with cathode
(up to 3V), after two electrodes are shorted or contact, cathode and metal lithium electrode form a pair of electrodes idol, and the two can occur spontaneous
Electrochemical reaction, lithium ion from metal lithium electrode dissolve, insert be embedded into cathode interlayer, namely without extra electric field in the case where, Li+I.e.
Cathode can be diffused to by electrolyte and to the embedding lithium of cathode.But due to inside battery core, between cathode and metal lithium electrode, especially
It is the battery core for being made of multi-disc pole piece, activation polarization is larger, this spontaneous pre- process of intercalation is very slow, and even up to 20
It.
The scheme of pre-embedding lithium method of the present invention is: after metal lithium electrode is mutually shorted with cathode, lithium metal dissolution, lithium ion into
Enter in lithium-ion electrolyte, can be embedded into the active material of cathode by diffusing to cathode and inserting.The diffusion time of lithium ion
It is proportional to L2/ D, i.e., it is square directly proportional to diffusion length L, it is inversely proportional with diffusion coefficient D, for lithium-ion energy storage device, expands
In the case where dissipating distance centainly, diffusion time can be shortened by improving diffusion effect.Therefore, while spontaneous short circuit pre- embedding lithium,
By applying charging process and discharge process between positive electrode and negative electrode, an extra electric field can be applied in device inside, from
And diffusion effect is improved, significantly shorten the pre- embedding lithium time.Meanwhile after metal lithium electrode is dissolved as lithium source, Li+Into electrolyte
In, lithium concentration can be maintained to stablize in electrolyte constant, be not to generate lithium ion and attempt the case where reducing, also do not need
Excessive electrolyte is added, additional lithium ion is provided.
The preparation method, the edge that the shell is equipped with the first pipe are sealed by the first heat-sealing device, institute
The remaining edge for stating shell is sealed by the second heat-sealing device.First heat-sealing device is equipped with being adapted to the first pipe
Groove body sealing die, second heat-sealing device be heat sealing machine.
The preparation method, the first pipe are metal tube or the modeling that the inner surface and the outer surface coats heat-sealable material
Expects pipe.The metal tube is stainless steel tube, nickel tube or aluminum pipe, and the plastic tube is PP pipe, PET pipe or PTFE tube.
The material of the preparation method, the first pipe is identical as heat-sealable material.
The preparation method, the internal diameter of the first pipe are 2-5mm, and the length being embedded in the shell is 5-
50mm。
The preparation method further includes separating the partial shell comprising the first pipe with remainder shell
Step.
The preparation method, heating temperature are 100-150 DEG C, and the time vacuumized is 12-72h, when injecting electrolyte
Pressure be -90~-30kPa.
Technical solution of the present invention has the advantages that
1. the preparation method of lithium ion electrochemical energy storage device provided by the invention, previously prepared placing into shell
The first pipe that pre-buried at least one is in communication with the outside when battery core and pretreated lithium electrode, in this way after sealing shell,
It is isolated from the outside in addition to the opening of first pipe, enclosure interior take out by the second pipe being connected to first pipe true
The sequence of operations such as empty, injection electrolyte and the extra rich solution of removal, so that whole operation is in isolation moisture and oxygen always
In environment, production efficiency is improved, the opening of last reheating envelope first pipe guarantees the overall performance of energy storage device.Due to system
Standby process has been compatible with existing equipment without carrying out in the space being fully sealed, and solves new type lithium ion electrification
Learn the technical problem that energy storage device is difficult to the large-scale production under existence conditions.
It is while being shorted the cathode of battery core and metal lithium electrode, the positive external power supply of battery core is positive, battery core
Cathode external power supply cathode makes Li by applying an electric field+It rapidly enters in electrolyte, improves diffusion effect, thus aobvious
It writes and shortens the pre- embedding lithium time.Meanwhile it can guarantee Li by applying electric field+Equably intercalation is avoided into the active constituent of cathode
Li+Performance (such as the capacity of the lithium ion electrochemical energy storage device brought by the uneven distribution in the active constituent of cathode
Conservation rate) decline；
Meanwhile the quality of lithium metal, cathode are living in the pre- lithium-inserting amount of the specific connection type and cathode, metal lithium electrode
Property cooperate at the thickness and positive-active of layering at thickness of layering etc., make electrochemical energy storing device that there is suitable charge and discharge
Electric system still has high capacity retention ratio to be conducive to device after multiple charge and discharge cycles.
2. the preparation method of lithium ion electrochemical energy storage device provided by the invention, further, by controlling charge and discharge
The parameter of processing shortens the time of pre- process of intercalation while guaranteeing that pre- process of intercalation is gone on smoothly, and improves device performance
(capacity retention ratio).Simultaneously by controlling the quality of lithium metal in metal lithium electrode according to specific formulation, have metal lithium electrode
Have the amount of suitable lithium metal, avoid the excessive very few influence to lithium ion electrochemical energy storage device performance, eventually by lithium from
Chemical energy is converted electric energy and storage energy by the embedding and ion transport process of inserting of son.
3. the preparation method of lithium-ion capacitor provided by the invention, first pipe indwelling in the housing, can also be rear
The approach of one multi-functional maintenance is provided in continuous use process, can effectively improve the circulation and items of energy storage device
Energy.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the structural schematic diagram of lithium ion electrochemical capacitor in the embodiment of the present invention；
Fig. 2 is the pre- process of intercalation schematic diagram of lithium ion electrochemical capacitor in the embodiment of the present invention；
Fig. 3 is that voltage changes with time in the pre- process of intercalation of lithium ion electrochemical capacitor in comparative example 1 of the present invention
Figure；
Fig. 4 is that voltage changes with time in the pre- process of intercalation of lithium ion electrochemical capacitor in the embodiment of the present invention 1
Figure；
Fig. 5 is that voltage changes with time in the pre- process of intercalation of lithium ion electrochemical capacitor in the embodiment of the present invention 2
Figure；
Wherein appended drawing reference indicates are as follows:
1- shell；20- metal lithium electrode collector；21- metallic lithium foil；3- diaphragm；40- plus plate current-collecting body；41- anode is living
Property is at layering；50- negative current collector；51- negative electrode active is at layering；6- positive pole ear；7- negative lug；8- power supply.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with specific embodiment, it is clear that retouched
The embodiment stated is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field
Those of ordinary skill's every other embodiment obtained without making creative work, belongs to protection of the present invention
Range.
As long as in addition, the non-structure each other of technical characteristic involved in invention described below different embodiments
It can be combined with each other at conflict.
As illustrated in fig. 1 and 2, cathode, diaphragm, anode, diaphragm are stacked gradually or is wound and form battery core, cathode is by cathode collection
Fluid 50 and the negative electrode active being arranged on are formed at layering 51, such as negative electrode active can be cathode coating, cathode at layering 51
Active ingredient layer 51 with a thickness of 20-90 microns, negative current collector 50 is copper foil with through hole or with through hole
The percent opening of nickel foil, the copper foil with through hole and the nickel foil with through hole is 2%-30%；Anode is by plus plate current-collecting body
40 and the positive-active that is arranged on formed at layering 41, such as positive-active can be positive coating at layering, positive-active at
20-150 microns of the thickness of layering, plus plate current-collecting body are the aluminium foil with through hole, and the percent opening of the aluminium foil with through hole is
2-30%；
It places metal lithium electrode in the outside of battery core again to be used to mend lithium, metal lithium electrode is by 20 He of metal lithium electrode collector
The metallic lithium foil 21 being arranged on forms, and is shorted metal lithium electrode mutually with cathode, and diaphragm 3 is used between metal lithium electrode and battery core
It separates；
Battery core, metal lithium electrode and diaphragm 3 are packaged in shell 1, while a pre-buried first pipe in the housing, the
One pipeline one end is placed in enclosure interior, and the other end extends shell and is connected to second pipe.Such as it is sealed with aluminum plastic film, and will just
Pole tab 6, negative lug 7 stretch out that shell 1 is outer and this two edge sealing, the sealing of another side, remain and next are equipped with the first pipe
The side in road is sealed by being equipped with the sealing die of groove body, appropriate to injection inside shell 1 by second pipe and first pipe
Electrolyte blocks being connected to for first pipe and second pipe after battery core sufficiently to infiltrate, with that is, anode and cathode are separately connected
The anode and cathode of power supply 8, such as power supply are charge-discharge test instrument.
Embodiment 1
First pipe is the pipeline for the PP material that internal diameter is 3mm, length is 20mm.The energy storage device after heat-sealing is put therewith
Enter in hot pressing formation device, the temperature of control hot pressing formation device is 120 DEG C, is then opened by valve on the second pipe
It opens and 48h is vacuumized to the enclosure interior, the moisture of enclosure interior is eliminated.Then by the after energy storage device natural cooling
Two pipelines carry out fluid injection to enclosure interior, and keep pressure for -70kPa to electrolyte complete wetting.Then the PP is blocked to manage
Road is connected to the second pipe, after carrying out pre- embedding lithium to the cathode of the battery core by electrochemical method, finally by lithium from
Anode, cathode and the lithium electrode of sub- energy storage device access charging/discharging apparatus, first with the electric current of 50mA to lithium-ion energy storage device
Cathode and lithium electrode carry out charge and discharge 5 times, then anode and cathode charge and discharge with the electric current of 100mA to lithium-ion energy storage device
5 times, it is then connected to PP pipeline and the second pipe again, opens second pipe valve, lithium ion is stored up by second pipe
Can device carry out degasification operation, then seal the opening of the first pipe other end, and disconnect the second pipe and described the
The connection of one pipeline obtains lithium ion electrochemical energy storage device.It is finally made under non-protective atmospheric condition through this embodiment
The lithium ion electrochemical energy storage device that standby capacity out is 500mAh.
The method of the pre- embedding lithium specifically:
Diaphragm is built up into Z-shaped, and by 1 anode, 1 cathode and 1 metal lithium electrode membranes apart, is done stacked
Chip battery core, cathode and metal lithium electrode are shorted, and are injected appropriate electrolyte and are sealed, by the anode of lithium ion electrochemical capacitor
It connects the anode and cathode of charge-discharge test instrument respectively with cathode, is charged with 0.03C electric current to device, charge to 4.1V after 4.3 days,
And shelve 24 hours, discovery metallic lithium foil is completely dissolved after disassembling device, and pre- process of intercalation is completed, be made after sealing again lithium from
Sub- electrochemical capacitor, as shown in Figure 4；
Wherein, positive positive-active ingredient is active carbon, and at 100 microns of thickness of layering 41, anode collects positive-active
Fluid is the aluminium foil with through hole that percent opening is 18%；
The negative electrode active ingredient of cathode is hard carbon, negative electrode active at layering 51 with a thickness of 60 microns, negative current collector 50
The copper foil with through hole for being 18% for percent opening；
Metal lithium electrode is covered for metallic lithium foil and is obtained on metal lithium electrode collector, and metal lithium electrode collector is tool
There is through hole copper foil；The quality of metallic lithium foil is m, and m meets following formula: m=3.6* (A*Q)/(F*Z), A are metallic lithium atoms
Amount, F Faraday constant, Z=1, Q are pre- embedding lithium capacity, and the unit of m is g, Q mAh；The pre- lithium-inserting amount of the cathode of battery core is negative
The 80% of pole capacity；
Electrolyte is the LiPF of 1mol/L6Solution, the solvent in electrolyte is the ethylene carbonate that volume ratio is 1:1:1
The mixed solvent of ester, dimethyl carbonate and diethyl carbonate.
Embodiment 2
First pipe is the pipeline identical with heat-seal adhesive material that internal diameter is 2mm, length is 50mm.After sealing therewith
Energy storage device be put into hot pressing formation device, the temperature of control hot pressing formation device is 100 DEG C, while being managed by described second
The unlatching of valve vacuumizes 72h to the enclosure interior on road, and the moisture of enclosure interior is eliminated.Then to energy storage device nature
Fluid injection is carried out to enclosure interior by second pipe after cooling, and keeps pressure for -90kPa to electrolyte complete wetting.Then
Being connected to for the first pipe and the second pipe is blocked, pre- embedding lithium is carried out by cathode of the electrochemical method to the battery core
Afterwards, the anode, cathode and lithium electrode of lithium-ion energy storage device are finally accessed into charging/discharging apparatus, first with the electric current of 50mA to lithium
The cathode and lithium electrode of ion energy storage device carry out charge and discharge 5 times, then with the electric current of 100mA to the anode of lithium-ion energy storage device
With cathode charge and discharge 5 times, be then connected to the first pipe and the second pipe again, open second pipe valve, pass through
Second pipe carries out degasification operation to lithium-ion energy storage device, then seals the opening of the first pipe other end, and disconnect institute
The connection of second pipe Yu the first pipe is stated, and the partial shell comprising the first pipe and remainder shell are divided
From obtaining lithium ion electrochemical energy storage device.Finally preparing capacity under non-protective atmospheric condition through this embodiment is
The lithium ion electrochemical energy storage device of 860mAh.
The method of the pre- embedding lithium specifically:
Diaphragm is built up into Z-shaped, and by 1 anode, 1 cathode and 1 metal lithium electrode membranes apart, is done stacked
Chip battery core, cathode and metal lithium electrode are shorted, and are injected appropriate electrolyte and are sealed, by the anode of lithium ion electrochemical capacitor
It connects the anode and cathode of charge-discharge test instrument respectively with cathode, 4.1V is charged to device with 3C electric current, with 3C electric current to device
It is discharged to 2.0V, is shelved 5 minutes, recycles 10 times, device is shelved, discovery voltage tends towards stability, and the electrochemical process of embedding lithium is complete
At, again seal after lithium ion electrochemical capacitor, such as Fig. 5 is made；
Wherein, positive positive-active ingredient is active carbon, and positive-active is at layering 50 microns of thickness of 41, anode collection
Body is the aluminium foil with through hole that percent opening is 28%；
The negative electrode active ingredient of cathode is graphite, negative electrode active at layering 51 with a thickness of 85 microns, negative current collector 50
The copper foil with through hole for being 5% for percent opening；
Metal lithium electrode is covered for metallic lithium foil and is obtained on metal lithium electrode collector, and metal lithium electrode collector is copper
Net；The quality of metallic lithium foil is m, and m meets following formula: m=3.6* (A*Q)/(F*Z), A are metallic lithium atoms amount, F faraday
Constant, Z 1, Q are pre- embedding lithium capacity, and the unit of m is g, Q mAh；The pre- lithium-inserting amount of the cathode of battery core is capacity of negative plates
80%；
Electrolyte is the LiPF of 1.0mol/L6Solution, the solvent in electrolyte is the ethylene carbonate that volume ratio is 1:1:1
The mixed solvent of ester, dimethyl carbonate and diethyl carbonate.
Embodiment 3
First pipe is the nickel tube that the outer surface that internal diameter is 5mm, length is 5mm and inner surface coat heat-seal adhesive.Therewith
Energy storage device after heat-sealing is put into hot pressing formation device, the temperature of control hot pressing formation device is 150 DEG C, while passing through institute
The unlatching for stating valve on second pipe vacuumizes 12h to the enclosure interior, and the moisture of enclosure interior is eliminated.Then to energy storage
Fluid injection is carried out to enclosure interior by second pipe after device natural cooling, and keeping pressure is that -30kPa soaks completely to electrolyte
Profit.Then being connected to for nickel tube and the second pipe is blocked, is carried out by positive or negative pole of the electrochemical method to the battery core
After pre- embedding lithium, the anode, cathode and lithium electrode of lithium-ion energy storage device are finally accessed into charging/discharging apparatus, first with the electricity of 50mA
It flows and the cathode and lithium electrode of lithium-ion energy storage device is carried out charge and discharge 5 times, then with the electric current of 100mA to lithium-ion energy storage device
Anode and cathode charge and discharge 5 times, be then connected to nickel tube and the second pipe again, open second pipe valve, by the
Two pipelines carry out degasification operation to lithium-ion energy storage device, then seal the opening of the first pipe other end, and described in disconnection
The connection of second pipe and the first pipe obtains lithium ion electrochemical energy storage device.Through this embodiment finally in non-guarantor
The lithium ion electrochemical energy storage device that capacity is 420mAh is prepared under shield property atmospheric condition.
The method of the pre- embedding lithium specifically:
With embodiment 2, the difference is that: the electric current of charge and discharge is 1C in pre- process of intercalation.
Embodiment 4
First pipe is the stainless steel tube that the outer surface that internal diameter is 4mm, length is 10mm and inner surface coat heat-seal adhesive.
The energy storage device after heat-sealing is put into hot pressing formation device therewith, the temperature of control hot pressing formation device is 120 DEG C, is led to simultaneously
The unlatching for crossing valve on the second pipe vacuumizes 60h to the enclosure interior, and the moisture of enclosure interior is eliminated.Then to
Fluid injection is carried out to enclosure interior by second pipe after energy storage device natural cooling, and keeping pressure is that -60kPa is complete to electrolyte
Full infiltration.Then block being connected to for stainless steel tube and the second pipe, by electrochemical method to the anode of the battery core or
After cathode carries out pre- embedding lithium, the anode, cathode and lithium electrode of lithium-ion energy storage device are finally accessed into charging/discharging apparatus, first with
The electric current of 100mA carries out the cathode and lithium electrode of lithium-ion energy storage device charge and discharge 5 times, then with the electric current of 300mA to lithium from
The anode of sub- energy storage device and cathode charge and discharge 5 times, are then connected to stainless steel tube and the second pipe again, open the second pipe
Road valve carries out degasification operation to lithium-ion energy storage device by second pipe, then seals opening for the first pipe other end
Mouthful, and the connection of the second pipe Yu the first pipe is disconnected, and by the partial shell comprising the first pipe and remain
The separation of remaining part housing parts, obtains lithium ion electrochemical energy storage device.Through this embodiment finally under non-protective atmospheric condition
Prepare the lithium ion electrochemical energy storage device that capacity is 1400mAh.
The method of the pre- embedding lithium specifically:
With embodiment 2, the difference is that: the electric current of charge and discharge is 5C in pre- process of intercalation.
Embodiment 5
First pipe is the PET pipe that the outer surface that internal diameter is 2mm, length is 20mm and inner surface coat heat-seal adhesive.With
The energy storage device after heat-sealing is put into hot pressing formation device, control hot pressing formation device temperature be 140 DEG C, then pass through
The unlatching of valve vacuumizes 25h to the enclosure interior on the second pipe, and the moisture of enclosure interior is eliminated.Then wait store up
Second pipe can be passed through to enclosure interior progress fluid injection after device natural cooling, and keeping pressure is that -40kPa is complete to electrolyte
Infiltration.Then PET pipe is blocked to be connected to the second pipe, by electrochemical method to the positive or negative pole of the battery core into
After the pre- embedding lithium of row, the anode, cathode and lithium electrode of lithium-ion energy storage device are finally accessed into charging/discharging apparatus, first with 50mA's
Electric current carries out the cathode and lithium electrode of lithium-ion energy storage device charge and discharge 5 times, then with the electric current of 100mA to lithium-ion energy storage device
Part anode and cathode charge and discharge 5 times, then again connection PET pipe and the second pipe, open second pipe valve, pass through
Second pipe carries out degasification operation to lithium-ion energy storage device, then seals the opening of the first pipe other end, and disconnect institute
The connection for stating second pipe Yu the first pipe obtains lithium ion electrochemical energy storage device.Through this embodiment finally non-
The lithium ion electrochemical energy storage device that capacity is 850mAh is prepared under the conditions of protective atmosphere.
The method of the pre- embedding lithium specifically:
With embodiment 2, the difference is that: the electric current of charge and discharge is 10C in pre- process of intercalation.
Embodiment 6
First pipe is 5mm, length is 30mm outer surface and inner surface coat the aluminum pipe of heat-seal adhesive.It therewith will heat-sealing
Energy storage device afterwards is put into hot pressing formation device, and the temperature of control hot pressing formation device is 130 DEG C, while passing through described second
The unlatching of valve vacuumizes 30h to the enclosure interior on pipeline, and the moisture of enclosure interior is eliminated.Then certainly to energy storage device
Fluid injection is so carried out to enclosure interior by second pipe after cooling, and keeps pressure for -70kPa to electrolyte complete wetting.So
Being connected to for aluminum pipe and the second pipe is blocked afterwards, and pre- embedding lithium is carried out by positive or negative pole of the electrochemical method to the battery core
Afterwards, the anode, cathode and lithium electrode of lithium-ion energy storage device are finally accessed into charging/discharging apparatus, first with the electric current pair of 100mA
The cathode and lithium electrode of lithium-ion energy storage device carry out charge and discharge 5 times, then with the electric current of 200mA to lithium-ion energy storage device just
Then pole and cathode charge and discharge 5 times are connected to aluminum pipe and the second pipe again, open second pipe valve, pass through the second pipe
Road carries out degasification operation to lithium-ion energy storage device, then seals the opening of the first pipe other end, and disconnect described second
The connection of pipeline and the first pipe obtains lithium ion electrochemical energy storage device.Through this embodiment finally in non-protective
The lithium ion electrochemical energy storage device that capacity is 590mAh is prepared under atmospheric condition.
The method of the pre- embedding lithium specifically:
With embodiment 2, the difference is that: the electric current of charge and discharge is 30C in pre- process of intercalation.
Embodiment 7
First pipe is the PTFE tube that the outer surface that internal diameter is 5mm, length is 40mm and inner surface coat heat-seal adhesive.With
The energy storage device after heat-sealing is put into hot pressing formation device, control hot pressing formation device temperature be 110 DEG C, pass through simultaneously
The unlatching of valve vacuumizes 40h to the enclosure interior on the second pipe, and the moisture of enclosure interior is eliminated.Then wait store up
Second pipe can be passed through to enclosure interior progress fluid injection after device natural cooling, and keeping pressure is that -50kPa is complete to electrolyte
Infiltration.Then being connected to for PTFE tube and the second pipe is blocked, by electrochemical method to the positive or negative pole of the battery core
After carrying out pre- embedding lithium, the anode, cathode and lithium electrode of lithium-ion energy storage device are finally accessed into charging/discharging apparatus, first with 50mA
Electric current the cathode and lithium electrode of lithium-ion energy storage device are carried out charge and discharge 5 times, then with the electric current of 200mA to lithium-ion energy storage
The anode of device and cathode charge and discharge 5 times, are then connected to PTFE tube and the second pipe again, open second pipe valve,
Degasification operation is carried out to lithium-ion energy storage device by second pipe, then seals the opening of the first pipe other end, and break
Open the connection of the second pipe Yu the first pipe, and by the partial shell comprising the first pipe and remainder shell
Body separation, obtains lithium ion electrochemical energy storage device.Appearance is finally prepared under non-protective atmospheric condition through this embodiment
Amount is the lithium ion electrochemical energy storage device of 1800mAh.
The method of the pre- embedding lithium specifically:
With 8 anodes, 9 cathode membranes aparts, it is made into Z-shaped lamination type electric core, by two such laminated batteries
Core is combined with 3 metal lithium electrodes by sandwich structure, and specific practice is: a lithium metal electricity is pressed from both sides among two battery cores
1 metal lithium electrode is respectively placed in pole, two sides, and cathode and metal lithium electrode are shorted, inject appropriate electrolyte and seal；By lithium ion
The anode and cathode of electrochemical capacitor connect the anode and cathode of charge-discharge test instrument respectively, are charged to 20C electric current to device
3.8V is discharged to 2.0V to device with 20C electric current, shelves 5 minutes, recycles 300 times；Then, device is charged to 20C electric current
4.1V is discharged to 2.0V to device with 20C electric current, shelves 5 minutes, recycles 200 times, and discovery metallic lithium foil is complete after disassembling device
Dissolution, pre- process of intercalation are completed, and lithium ion electrochemical capacitor is made after sealing again；
Wherein, just extremely double-face electrode, positive-active ingredient are active carbon, and positive-active is at the thickness for being layered 41 single sides
120 microns, plus plate current-collecting body is the aluminium foil with through hole that percent opening is 5%；
Cathode is double-face electrode, and negative electrode active ingredient is hard carbon, negative electrode active at 51 single sides of layering with a thickness of 25 microns,
Negative current collector 50 is the nickel foil with through hole that percent opening is 28%；
Metal lithium electrode is covered for metallic lithium foil and is obtained on metal lithium electrode collector, and metal lithium electrode collector is nickel
Net；The quality of metallic lithium foil is m, and m meets following formula: m=3.6* (A*Q)/(F*Z), A are metallic lithium atoms amount, F faraday
Constant, Z 1, Q are pre- embedding lithium capacity, and the unit of m is g, Q mAh；The pre- lithium-inserting amount of the cathode of battery core is capacity of negative plates
80%；
Electrolyte is the LiPF of 1mol/L6Solution, the solvent in electrolyte is the ethylene carbonate that volume ratio is 1:1:1
The mixed solvent of ester, dimethyl carbonate and diethyl carbonate.
Embodiment 8
First pipe is 3mm, length is 30mm outer surface and inner surface coat the aluminum pipe of heat-seal adhesive.It therewith will heat-sealing
Energy storage device afterwards is put into hot pressing formation device, and the temperature of control hot pressing formation device is 140 DEG C, while passing through described second
The unlatching of valve vacuumizes 50h to the enclosure interior on pipeline, and the moisture of enclosure interior is eliminated.Then certainly to energy storage device
Fluid injection is so carried out to enclosure interior by second pipe after cooling, and keeps pressure for -80kPa to electrolyte complete wetting.So
Being connected to for aluminum pipe and the second pipe is blocked afterwards, and pre- embedding lithium is carried out by positive or negative pole of the electrochemical method to the battery core
Afterwards, the anode, cathode and lithium electrode of lithium-ion energy storage device are finally accessed into charging/discharging apparatus, first with the electric current pair of 100mA
The cathode and lithium electrode of lithium-ion energy storage device carry out charge and discharge 5 times, then with the electric current of 200mA to lithium-ion energy storage device just
Then pole and cathode charge and discharge 5 times are connected to aluminum pipe and the second pipe again, open second pipe valve, pass through the second pipe
Road carries out degasification operation to lithium-ion energy storage device, then seals the opening of the first pipe other end, and disconnect described second
The connection of pipeline and the first pipe obtains lithium ion electrochemical energy storage device.Through this embodiment finally in non-protective
The lithium ion electrochemical energy storage device that capacity is 630mAh is prepared under atmospheric condition.
The method of the pre- embedding lithium specifically:
Diaphragm is built up into Z-shaped, and by 1 anode, 1 cathode and 1 metal lithium electrode membranes apart, is done stacked
Chip battery core, cathode and metal lithium electrode are shorted, and are injected appropriate electrolyte and are sealed, by the anode of lithium ion electrochemical capacitor
It connects the anode and cathode of charge-discharge test instrument respectively with cathode, 4.2V is charged to the electric current of 0.25C, then with 4.2V constant-voltage charge
For 24 hours, discovery metallic lithium foil is completely dissolved after disassembling device, and pre- process of intercalation is completed, and lithium ion electrochemical is made after sealing again
Capacitor；
Wherein, positive positive-active ingredient is active carbon, and positive-active is at layering 50 microns of thickness of 41, anode collection
Body is the aluminium foil with through hole that percent opening is 28%；
The negative electrode active ingredient of cathode is graphite, negative electrode active at layering 51 with a thickness of 85 microns, negative current collector 50
For percent opening be 5% copper foil with through hole or with the nickel foil of through hole；
Metal lithium electrode is covered for metallic lithium foil and is obtained on metal lithium electrode collector, and metal lithium electrode collector is copper
Net；The quality of metallic lithium foil is m, and m meets following formula: m=3.6* (A*Q)/(F*Z), A are metallic lithium atoms amount, F faraday
Constant, Z 1, Q are pre- embedding lithium capacity, and the unit of m is g, Q mAh；The pre- lithium-inserting amount of the cathode of battery core is capacity of negative plates
85%；
Electrolyte is the solution of the LiBF4 of 1.5mol/L, and the solvent in electrolyte is the carbon that volume ratio is 1:1:1
The mixed solvent of acid propylene ester, vinylene carbonate and diethyl carbonate.
Embodiment 9
First pipe is the PET pipe that the outer surface that internal diameter is 4mm, length is 50mm and inner surface coat heat-seal adhesive.With
The energy storage device after heat-sealing is put into hot pressing formation device, control hot pressing formation device temperature be 130 DEG C, then pass through
The unlatching of valve vacuumizes 35h to the enclosure interior on the second pipe, and the moisture of enclosure interior is eliminated.Then wait store up
Second pipe can be passed through to enclosure interior progress fluid injection after device natural cooling, and keeping pressure is that -40kPa is complete to electrolyte
Infiltration.Then PET pipe is blocked to be connected to the second pipe, by electrochemical method to the positive or negative pole of the battery core into
After the pre- embedding lithium of row, the anode, cathode and lithium electrode of lithium-ion energy storage device are finally accessed into charging/discharging apparatus, first with 50mA's
Electric current carries out the cathode and lithium electrode of lithium-ion energy storage device charge and discharge 5 times, then with the electric current of 100mA to lithium-ion energy storage device
Part anode and cathode charge and discharge 5 times, then again connection PET pipe and the second pipe, open second pipe valve, pass through
Second pipe carries out degasification operation to lithium-ion energy storage device, then seals the opening of the first pipe other end, and disconnect institute
The connection for stating second pipe Yu the first pipe obtains lithium ion electrochemical energy storage device.Through this embodiment finally non-
The lithium ion electrochemical energy storage device that capacity is 1200mAh is prepared under the conditions of protective atmosphere.
The method of the pre- embedding lithium specifically:
Diaphragm is built up into Z-shaped, and by 1 anode, 1 cathode and 1 metal lithium electrode membranes apart, is done stacked
Chip battery core, cathode and metal lithium electrode are shorted, and are injected appropriate electrolyte and are sealed, by the anode of lithium ion electrochemical capacitor
It connects the anode and cathode of charge-discharge test instrument respectively with cathode, 3.8V is charged to the electric current of 0.5C, then with 3.8V constant-voltage charge
0.5h, then with the current discharge of 0.1C to 2.0V, be so repeated 5 times, discovery metallic lithium foil is completely dissolved after disassembling device, pre- embedding
Lithium process is completed, and lithium ion electrochemical capacitor is made after sealing again；
Wherein, positive positive-active ingredient is LiFePO4, and at 80 microns of thickness of layering 41, anode collects positive-active
Fluid is the aluminium foil with through hole that percent opening is 22%；
The negative electrode active ingredient of cathode is carbonaceous mesophase spherules and aoxidizes sub- silicon, and the mass ratio of the two is 99.5:0.5, is born
Pole active ingredient layer 51 with a thickness of 30 microns, negative current collector 50 is the copper foil with through hole that percent opening is 15%；
Metal lithium electrode is covered for metallic lithium foil and is obtained on metal lithium electrode collector, and metal lithium electrode collector is bubble
Foam metallic nickel；The quality of metallic lithium foil is m, and m meets following formula: m=3.6* (A*Q)/(F*Z), A are metallic lithium atoms amount, F
Faraday constant, Z 1, Q are pre- embedding lithium capacity, and the unit of m is g, Q mAh；The pre- lithium-inserting amount of the cathode of battery core is cathode appearance
The 10% of amount；
Electrolyte is the solution of the lithium perchlorate of 0.5mol/L, and the solvent in electrolyte is the carbonic acid that volume ratio is 1:1:1
The mixed solvent of acrylic ester, vinylene carbonate and ethylene carbonate.
Comparative example 1
The method of the pre- embedding lithium specifically:
1) diaphragm is built up into Z-shaped, and by 1 anode, 1 cathode and 1 metal lithium electrode membranes apart, be made into
Lamination type electric core, cathode and metal lithium electrode are shorted, and are injected appropriate electrolyte and are sealed, lithium ion electrochemical capacitor is made；
Wherein, positive positive-active ingredient is active carbon, and at 100 microns of thickness of layering 41, anode collects positive-active
Fluid is the aluminium foil with through hole that percent opening is 18%；
The negative electrode active ingredient of cathode is hard carbon, negative electrode active at layering 51 with a thickness of 60 microns, negative current collector 50
The copper foil with through hole for being 18% for percent opening；
Metal lithium electrode is covered for metallic lithium foil and is obtained on metal lithium electrode collector, and metal lithium electrode collector is tool
There is through hole copper foil；The quality of metallic lithium foil is m, and m meets following formula: m=3.6* (A*Q)/(F*Z), A are metallic lithium atoms
Amount, F Faraday constant, Z 1, Q are pre- embedding lithium capacity, and the unit of m is g, Q mAh；The pre- lithium-inserting amount of the cathode of battery core is negative
The 80% of pole capacity；
Electrolyte is the LiPF of 1mol/L6Solution, the solvent in electrolyte is the ethylene carbonate that volume ratio is 1:1:1
The mixed solvent of ester, dimethyl carbonate and diethyl carbonate；
2) cell tester for using Wuhan Lan electricity company CT2001A, monitors positive and negative pole tension, and not external charge and discharge electrical measurement
It tries instrument and carries out charge or discharge operation, as shown in figure 3, the carry out voltage with pre- process of intercalation gradually rises, after shelving 10.5 days
Voltage reaches 2.8V and tends towards stability, and pre- process of intercalation is completed.
Other steps are same as Example 1.
Comparative example 2
The method of the pre- embedding lithium specifically:
1) diaphragm is built up into Z-shaped, and by 1 anode, 1 cathode and 1 metal lithium electrode membranes apart, be made into
Lamination type electric core, cathode and metal lithium electrode are shorted, and are injected appropriate electrolyte and are sealed, lithium ion electrochemical capacitor is made,
Charge-discharge test is carried out after placing 20 days；
Wherein, positive positive-active ingredient is active carbon, and at 100 microns of thickness of layering 41, anode collects positive-active
Fluid is the aluminium foil with through hole that percent opening is 18%；
The negative electrode active ingredient of cathode is hard carbon, negative electrode active at layering 51 with a thickness of 60 microns, negative current collector 50
The copper foil with through hole for being 18% for percent opening；
Metal lithium electrode is covered for metallic lithium foil and is obtained on metal lithium electrode collector, and metal lithium electrode collector is tool
There is through hole copper foil；The quality of metallic lithium foil is m, and m meets following formula: m=3.6* (A*Q)/(F*Z), A are metallic lithium atoms
Amount, F Faraday constant, Z=1, Q are pre- embedding lithium capacity, and the unit of m is g, Q mAh；The pre- lithium-inserting amount of the cathode of battery core is negative
The 80% of pole capacity；
Electrolyte is the LiPF of 1mol/L6Solution, the solvent in electrolyte is the ethylene carbonate that volume ratio is 1:1:1
The mixed solvent of ester, dimethyl carbonate and diethyl carbonate.
Other steps are same as Example 1.
Comparative example 3
This comparative example using embodiment 9 in Chinese patent literature CN 103915262A pre-embedding lithium method, other steps with
Embodiment 1 is identical.
Comparative example 4
This comparative example using embodiment 3 in Chinese patent literature CN 104681311A pre-embedding lithium method, other steps with
Embodiment 1 is identical.
Test example 1
Since a small amount of gas can be generated in pre- process of intercalation, causes to be bonded not tight, activation polarization between pole piece and increase, is interior
Resistance increases, therefore need to carry out a vacuum seal to embodiment 1-9 and comparative example 1-4 obtained device finally, obtains finished product
Lithium ion electrochemical energy storage device, then charge and discharge are carried out to it with 5C and 10C respectively, record its capacity retention ratio, wherein capacity
Conservation rate is the capacity after recycling and the ratio between initial capacity, characterizes the cyclical stability of device.As a result such as the following table 1 institute
Show:
Table 1
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (9)
1. a kind of preparation method of lithium ion electrochemical energy storage device characterized by comprising
The cathode of battery core and metal lithium electrode are shorted, and between the battery core and metal lithium electrode setting both separate every
The battery core, metal lithium electrode and diaphragm are packaged in shell by film；The cathode is by negative current collector and is arranged on negative
Pole active ingredient layer composition, the negative electrode active is at layering with a thickness of 20-90 microns；The anode of the battery core is by anode collection
Body and the positive-active being arranged on are formed at layering, and the positive-active is at 20-180 microns of thickness of layering；
The pre-buried at least one first pipe in the shell, one end of the first pipe is placed in the enclosure interior, another
End is extended the shell and is connected to second pipe, and the shell is sealed；
The enclosure interior is vacuumized by the second pipe, injects electrolyte, blocks the first pipe and described the
The connection of two pipelines carries out pre- embedding lithium by cathode of the electrochemical method to the battery core；
After the anode is connected to the cathode progress charge and discharge, be connected to again the first pipe and the second pipe into
Row pumping, seals the opening of the first pipe other end, and disconnect the connection of the second pipe Yu the first pipe, obtains
To lithium ion electrochemical energy storage device；
The method of the pre- embedding lithium are as follows:
By the positive external power supply of battery core anode, the cathode external power supply cathode of the battery core, to carry out after once charging
Primary electric discharge is as a circulation or after being shelved after once charging as a circulation or with constant current charge
Constant voltage charging is carried out as a circulation, charge and discharge electric treatment is carried out to the cathode of the battery core, completes the cathode of the battery core
Pre- embedding lithium；
The quality of lithium metal is m in the metal lithium electrode, and m meets following formula:
M=3.6* (A*Q)/(F*Z), wherein the unit of m is g, and A is metallic lithium atoms amount, and unit g/mol, F faraday is normal
Number, Z=1, Q are pre- embedding lithium capacity, and value is the 10-90% of capacity of negative plates, and the unit of Q is mAh.
2. preparation method according to claim 1, which is characterized in that the number of the circulation is 1-500 times.
3. preparation method according to claim 1, which is characterized in that the charge and discharge electric treatment is with the electricity of 0.01-0.5C
Current charge shelves 1-24h to upper limit voltage；
Alternatively, the charge and discharge electric treatment is with the electric current of 0.01-0.5C to charge to upper limit voltage, then with upper limit voltage constant-voltage charge
1-24h；
Alternatively, the charge and discharge electric treatment is with the electric current of 0.01-0.5C to charge to upper limit voltage, then with upper limit voltage constant-voltage charge
0.1-1h, then with the current discharge of 0.01-0.5C to blanking voltage, so repeat 1-10 times；
Alternatively, the charge and discharge electric treatment is to charge to upper limit voltage with the electric current of 1-30C, then extremely cut with the current discharge of 1-30C
Only voltage shelves 1-10min, so repeats 10-500 times.
4. preparation method according to claim 3, which is characterized in that the upper limit voltage is 3.8-4.2V；The cut-off
Voltage is 2.0-2.5V.
5. the preparation method according to claim 4, which is characterized in that the negative electrode active at the negative electrode active in layering at
It is divided at least one of graphite, carbonaceous mesophase spherules, hard carbon, soft carbon, the sub- silicon of oxidation, nanocrystal silicon；
The positive-active is nickle cobalt lithium manganate, nickel cobalt lithium aluminate, cobalt acid lithium, ferric phosphate at the positive-active ingredient in layering
At least one of lithium, porous carbon materials；
The metal lithium electrode collector is with through hole copper foil, has through hole nickel foil, copper mesh, nickel screen, foam metal copper
Or foam metal nickel.
6. preparation method according to claim 1, which is characterized in that the metal lithium electrode is by metal lithium electrode collector
With the metallic lithium foil composition being arranged on.
7. preparation method according to claim 1, which is characterized in that the negative current collector is the copper foil with through hole
Or the nickel foil with through hole；The plus plate current-collecting body is the aluminium foil with through hole.
8. preparation method according to claim 1, which is characterized in that further include the part shell that will include the first pipe
The step of body is separated with remainder shell.
9. preparation method according to claim 1, which is characterized in that heating temperature is 100-150 DEG C, the time vacuumized
For 12-72h, pressure when injecting electrolyte is -90~-30kPa.
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Inventor after: An Yabin Inventor after: Ma Yanwei Inventor after: Sun Xianzhong Inventor after: Zhang Xiong Inventor before: An Yabin Inventor before: Ma Yanwei Inventor before: Sun Xianzhong Inventor before: Zhang Xiong |