CN100595965C - Li-ion secondary battery formation method - Google Patents
Li-ion secondary battery formation method Download PDFInfo
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- CN100595965C CN100595965C CN200710112481A CN200710112481A CN100595965C CN 100595965 C CN100595965 C CN 100595965C CN 200710112481 A CN200710112481 A CN 200710112481A CN 200710112481 A CN200710112481 A CN 200710112481A CN 100595965 C CN100595965 C CN 100595965C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a formation method of a lithium ion second battery. The method includes the steps that: electrolyte is injected into the lithium ion second battery, the battery is charged upat the formation temperature of the lithium ion second battery. The charging method includes a first charging process and a second charging process. After the first charging process, the electrolyte is once more injected into the lithium ion second battery, wherein, the total quantity of the electrolyte injected before and after the first charge process is adopted as benchmark, the proportion of the electrolyte injected before the first charge process accounts for 50 percent to 80 percent of the total weight, and the proportion of the electrolyte injected after the first charge process accounts for 20 percent to 50 percent of the total weight. The anode active substance of the lithium ion second battery is lithium iron phosphate. The method is particularly applicable to the lithium ion second battery, the anode active substance of which is lithium iron phosphate, can effectively improve the capacity of the battery, and also enhance the circulation performance and heavy current discharge performance of the battery.
Description
Technical field
The invention relates to a kind of chemical synthesizing method of battery, specifically, the invention relates to a kind of chemical synthesizing method of lithium rechargeable battery.
Background technology
The step that changes into of lithium ion secondary rechargeable battery is to make the important stage of battery, changes into many-sided qualities such as the capacity height that is related to battery, cycle life length, security performance.Change into the process of battery being carried out initial charge that is meant.Changing into of existing lithium rechargeable battery mainly contains dual mode, seals to change into opening to change into.Seal change into be after having annotated electrolyte with liquid injection hole sealing, carry out battery then and change into, form negative terminal surface SEI film (Solid ElectrolyteInterface) by electrochemical reaction in the charging simultaneously.But owing in the forming process of SEI film, can produce a part of gas, such as hydrogen fluoride, carbon monoxide, carbon dioxide, nitric oxide, ethene and divinyl etc.Because the battery case liquid injection hole is closed, the gas that produces in the formation process can not be discharged timely, and gas limited space quilt accumulation slowly in battery case just causes cell expansion like this, shell swell, distortion, even can cause battery to be blasted.In order to overcome this problem, adopt another kind of mode to change in the prior art usually, promptly under the unencapsulated situation in battery liquid-filling hole, battery is changed into, treat that battery seals liquid injection hole after changing into again, promptly opening changes into.
Existing chemical synthesizing method about lithium rechargeable battery mainly is at adopting LiCoO
2Just be subjected to the LiNiO of extensive concern
2, LiMnO
4Chemical synthesizing method on the battery of positive active material preparation.In the formation process of lithium rechargeable battery, organic electrolyte can reduce, decompose in the carbon negative terminal surface, the passivation layer SEI film (Surface ElectrolyteInterface) that formation one deck electronic isolation, lithium ion can be led.Because the telescopiny of lithium ion is inevitable via the SEI film that covers on the carbon negative pole, therefore the characteristic of SEI film is to the chemical property of entire lithium ion battery, as battery capacity, the faradic efficiency of battery, cycle life, self-discharge performance (storage life), cryogenic property, stability and fail safe etc. all have very big influence, all even stable SEI film can adapt to the embedding of lithium ion and the stereomutation of deviating to cause well, therefore all even stable SEI film of formation all is favourable to the various chemical properties of battery, therefore, the characteristic of SEI film depends on directly that then battery changes into the whether proper of preparation method.
The chemical synthesizing method of disclosed lithium rechargeable battery once injects whole electrolyte required in the battery manufacturing process in the battery case normally before battery changes in the prior art, and charging then changes into.The purpose of once injecting whole electrolyte is for the electrolyte in the capacity of formation process assurance first, so that electrolyte is fully wetting with pole piece, make polarization less, do not influence the formation of pole piece surface SEI film, adopt in the process that this method changes into battery, be easy to occur problem in the dead of night, and too much cause the battery case internal gas pressure excessive owing to gas produces, make battery case that irreversible elastic deformation take place, influence the attractive in appearance of the chemical property of battery and housing.
Therefore, the method that twice injection of employing electrolyte changes into for twice in the existing method is generally the electrolyte that injects the 85-90 weight % of electrolyte total amount ratio before charging changes into for the first time, carry out changing into the first time, and then inject the 10-15 weight % of electrolyte total amount ratio and change into the second time of carrying out subsequently.Though adopt above-mentioned chemical synthesizing method to solve because inside battery air pressure increases the problem that causes that the air pressure protective device is opened too early; a part of gas is discharged from liquid injection hole in charging process; reduce the generation of inside battery gas to a certain extent; but battery still the leakage problem can occur; adopt the passivation layer SEI film that forms in the carbon negative terminal surface in the process that this method changes into battery not to be sufficiently complete and evenly, therefore combination properties such as the cycle performance of lower, the battery of the capacity of the lithium rechargeable battery that obtains and heavy-current discharge performance are still not satisfactory.In addition, it is the lithium rechargeable battery that positive active material prepares that the prior art disclosed method all is not suitable for being applied to the LiFePO 4, after changing into, be the not obviously improvement of lithium rechargeable battery comprehensive electrochemical of positive active material with the LiFePO 4.
Summary of the invention
The objective of the invention is to overcome that existing chemical synthesizing method is not suitable for being applied to the LiFePO 4 is the lithium rechargeable battery that positive active material obtains, change into the unfavorable shortcomings of comprehensive electrochemical such as back cycle performance of battery and heavy-current discharge performance, provide that a kind of what make that battery has good circulation performance and heavy-current discharge performance is the chemical synthesizing method of the lithium rechargeable battery of positive active material with the LiFePO 4.
The present inventor is surprised to find that, adopting secondary of the present invention to inject the mode of electrolyte, limit the ratio of twice injection electrolyte, the electrolyte that injects for the first time can fully be soaked into electrode active material, formation homogeneous, the stable SEI film of part in first time charging process, then by re-inject electrolyte and the second time charging process finally form and obtain complete, homogeneous, stable SEI film.This method has not only solved electrolyte and has once injected too much problem in the corresponding increase of a formation process leaking liquid amount, greatly reduced the fluid injection difficulty, guarantee the electrolyte residual quantity of battery, the thickness of battery is controlled effectively, it is the lithium rechargeable battery of positive active material that this method is specially adapted to the LiFePO 4, can effectively improve the capacity of battery, improve the cycle performance and the heavy-current discharge performance of battery.
The invention provides a kind of chemical synthesizing method of lithium rechargeable battery, this method comprises injects electrolyte in lithium rechargeable battery, changing under the temperature of lithium rechargeable battery battery is charged then, described charging method comprises charging process and charging process for the first time for the second time, in lithium rechargeable battery, inject electrolyte in the first time once more after the charging process, wherein, total amount with electrolyte that injects before the charging process first time and the electrolyte that injects after the charging process first time is a benchmark, the ratio of the electrolyte that injects before the charging process in the first time is 50-80 weight %, and the ratio of the electrolyte that injects after the charging process in the first time is 20-50 weight %; Described lithium rechargeable battery is that positive active material is the lithium rechargeable battery of LiFePO 4.
The secondary fluid injection of lithium rechargeable battery of the present invention, it is complete that the method that secondary changes into can make organic electrolyte form one deck in the carbon negative terminal surface, homogeneous, stable passivation layer SEI film, this method has not only solved electrolyte and has once injected too much problem in the corresponding increase of a formation process leaking liquid amount, greatly reduced the fluid injection difficulty, guarantee the electrolyte residual quantity of battery, cell thickness is controlled effectively, and it is the lithium rechargeable battery of positive active material that this method is specially adapted to the LiFePO 4, can effectively improve the capacity of battery, improve the cycle performance and the heavy-current discharge performance of battery.
Embodiment
According to the present invention, this method comprises injects electrolyte in lithium rechargeable battery, changing under the temperature of lithium rechargeable battery battery is charged then, described charging method comprises charging process and charging process for the first time for the second time, in lithium rechargeable battery, inject electrolyte in the first time once more after the charging process, wherein, total amount with electrolyte that injects before the charging process first time and the electrolyte that injects after the charging process first time is a benchmark, the ratio of the electrolyte that injects before the charging process in the first time is 50-80 weight %, be preferably 55-less than 70 weight %, the ratio of the electrolyte that injects after first time charging process is 20-50 weight %, is preferably more than 30-45 weight %; Described lithium rechargeable battery is that positive active material is the lithium rechargeable battery of LiFePO 4.
According to method of the present invention, total amount with electrolyte that injects before the charging process first time and the electrolyte that injects after the charging process first time is a benchmark, the ratio of the electrolyte that injects before the charging process in the first time is 50-80 weight %, be preferably 55-less than 70 weight %, if the electrolyte content that injects is very few for the first time, as, be less than 50%, then the quantity not sufficient of electrolyte is caused the internal resistance of cell big so that electrode slice soaks into fully, because positive active material LiFePO
4Than LiCoO
2Low conductivity, therefore, the polarization of battery is also bigger, thereby influences the formation of SEI film in the formation process; If the electrolyte content that injects is too much for the first time, as 85-90 weight %, though electrolyte can fully soak into electrode slice, reduce polarization, but battery is in the dead of night serious in formation process, can cause the significant wastage of electrolyte, more seriously, because the battery case air pressure inside is bigger, organic electrolyte is not easy to form SEI film complete, homogeneous in the carbon negative terminal surface, thereby therefore the chemical property of battery also is affected, in addition, the battery container air pressure inside is excessive, can make battery case that irreversible elastic deformation takes place, and makes the thickness of finished product battery be difficult to effective control.And the present invention adopts the 50-80 weight % that injects the total amount ratio of electrolyte for the first time, be preferably 55-less than 70 weight %, can guarantee that promptly electrolyte can fully soak into electrode active material, can effectively reduce polarization again, thereby the formation homogeneous of part in first time charging process, stable SEI film, the 20-50 weight % of the total amount ratio by re-injecting electrolyte then, be preferably more than the electrolyte of 30-45 weight %, replenished the electrolyte consumption of battery in follow-up use on the one hand, can guarantee again battery the second time charging process finally form and obtain complete, homogeneous, stable SEI film is very beneficial for the improvement of battery comprehensive electrochemical.
The battery of every kind of model all can calculate the design capacity of battery according to the amount of positive and negative electrode active material, total injection rate of electrolyte then can be determined reservoir quantity according to the production technology of routine, also can determine according to the design capacity of battery, for example, total injection rate of described electrolyte is generally 2.5-5 gram/ampere-hour.
The kind of described electrolyte is conventionally known to one of skill in the art, the electrolyte of lithium rechargeable battery is nonaqueous electrolytic solution, described nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and it is not particularly limited, and can use the nonaqueous electrolytic solution of this area routine.Be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), in lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more.Organic solvent is selected chain acid esters and ring-type acid esters mixed solution for use, wherein the chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other are fluorine-containing, sulfur-bearing or contain at least a in the chain organosilane ester of unsaturated bond, the ring-type acid esters can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other are fluorine-containing, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond.The concentration of described electrolyte be generally 0.1-2.0 rub/liter.
According to the present invention, described first time, charging process comprised with first electric current constant current charge to the first voltage, described second time, charging process comprised that described second voltage is higher than first voltage with second electric current constant current charge to the second voltage, and described second electric current is more than or equal to first electric current.
Described second voltage is higher than at least 0.1 volt of first voltage, and described second electric current is greater than first electric current 0.005C at least.
Described first electric current is 0.01-0.5C, is preferably 0.01-0.2C; Described first voltage is the 3.0-3.5 volt; Described second electric current is 0.01-1.0C, is preferably 0.05-1.0C; Described second voltage is the 3.5-4.0 volt.Described size of current is defined as conventionally known to one of skill in the art, for example, prepares the battery that design capacity is 800 MAHs, refers to promptly that with the current charges of 1C the electric current with 800 milliamperes charges to battery; 0.005C electric current promptly refer to 4 milliamperes electric current.
Under the optimum condition, this method is included in after the charging process first time, under vacuum condition, injects electrolyte in lithium rechargeable battery, and described vacuum degree is the 0.04-0.1 MPa, is preferably the 0.06-0.1 MPa.Above-mentioned vacuum degree is defined as the absolute value of the difference of absolute pressure and atmospheric pressure.
Because after charging for the first time, inside battery can residually have portion gas, can increase the difficulty of secondary fluid injection, and the thickness of battery is increased, in order to reduce the fluid injection difficulty, improve fluid injection efficient, reduce cell thickness, therefore, after first time charging process, preferably under vacuum condition, in lithium rechargeable battery, inject electrolyte once more.The method of described maintenance vacuum degree can adopt the method for well known to a person skilled in the art, vacuum condition of the present invention preferably vacuumizes formation to battery, as the method that adopts vacuum extractor to vacuumize, the described method that vacuumizes can vacuumize the method for marginal not liquid for step limit, also can be for vacuumizing and once will remain the method that electrolyte all injects continuously.
According to the present invention, this method also is included in to be injected in lithium rechargeable battery for the second time after the electrolyte, the aging step before second time charging process, and the temperature of described ageing is 30-80 ℃, the time of ageing is 5-130 hour.Described ageing can make the electrolyte that injects for the second time fully mix with the electrolyte that injects for the first time, soaks into positive/negative plate simultaneously.
According to the present invention, in order to make the SEI film that forms in the formation process more stable, this method also is included in charging process aging step afterwards for the second time, and the temperature of described ageing is 30-80 ℃, and the time of ageing is 5-130 hour.
Generally speaking, before first time charging process, in battery, inject electrolyte first after, preferably with battery under 35-55 ℃, placed 12-60 hour, more even, fine and close to reach the purpose that makes electrolyte fully soak into electrode active material in the electric core, to make the SEI film that forms in the formation process.
The temperature that changes into of described lithium rechargeable battery is generally at room temperature and carries out, as can for 20-less than 30 ℃.
But, for positive active material LiFePO
4, because at LiFePO
4Structure in, FeO
6Octahedron is positioned at the PO of its interlayer
4Tetrahedron is separated, thereby makes LiFePO
4Electron conductivity lower; Simultaneously, LiFePO
4Oxygen atom in the crystal is arranged to approach the closelypacked mode of six sides, can only provide limited passage for lithium ion, has finally hindered lithium ion migration therein, and is LiFePO with the positive active material
4Lithium ion battery because LiFePO
4(in room temperature, its conductivity only is 10 the lower problem of conductivity
-8S/cm, and LiCoO
2And LiMn
2O
4Be respectively 10
-3S/cm and 10
-4S/cm), influenced lithium ion diffusion therein, and the charge and discharge process of ferrous phosphate lithium ion battery is a diffusion-controlled step, the result has just caused ferrous phosphate lithium ion battery more serious polarization problem in charging process, and polarization will directly influence the quality of the SEI film that forms in the formation process, and then influence changes into every performance of battery afterwards.
And the present inventor finds, is LiFePO in the method that adopts secondary injection electrolyte of the present invention, secondary to change into to positive active material
4Lithium rechargeable battery change into, and preferably under hot conditions, for example 35-80 ℃, preferably under 35-60 ℃, when battery is changed into, can improve the migration rate of lithium ion, effectively reduce the degree of polarization that causes owing to material electric conductivity is low in the battery formation process, thereby effectively promote the formation of SEI film in the ferrous phosphate lithium ion battery formation process.The temperature that improves simultaneously environment in formation process can reduce in the formation process viscosity of electrolyte in the battery, improve the ions diffusion ability of electrolyte, form good ion migration environment, improve the ion migration rate in the formation process, thereby improved the migration rate of iron cell, so just can effectively reduce because positive active material LiFePO
4Than LiCoO
2The low polarization that conductivity caused can effectively form more complete SEI film in formation process, improve the utilance of material.Thereby when improving the capacity of lithium ion battery that positive active material is a LiFePO4, can also improve the cycle performance and the multiplying power discharging property of battery.
In addition, the method that present formation process all adopts opening to change into, if too much electrolyte is injected in fluid injection so for the first time, as injecting for the first time the electrolyte of electrolyte total weight more than 80%, reach 90% electrolyte, in formation process first owing to be accompanied by the formation electrolyte of SEI film and also decompose, make the battery case internal gas pressure increase, gas also can partly be gushed out simultaneously, comprehensive above-mentioned reason makes the electrolyte in the battery case partly to overflow, cause the minimizing of battery electrolyte inside, the minimizing of electrolyte can hinder the migration velocity of lithium ion in battery, increased on the negative plate and can not get back to the quantity of the lithium ion on the positive plate freely, thereby increased irreversible capacity, and be unfavorable for that negative terminal surface forms uniform and stable SEI film, cause battery polarization, the internal resistance of cell increases, and battery capacity reduces, and the cycle life of battery is affected.Overflowing of electrolyte also makes battery-shell surface be corroded simultaneously, influences the aesthetic measure of battery; If the electrolyte that injects just can not guarantee that pole piece is soaked into fully very little for the first time, cause pole piece active material LiFePO
4Change into not exclusively.
Therefore, the method that secondary fluid injection secondary of the present invention changes into, and the method that preferably at high temperature changes into is particularly suitable for being applied to LiFePO 4 as the lithium rechargeable battery that positive active material prepares, after changing into, the improvement of battery performance is obvious.
According to the present invention, the described method that changes into is included in the battery container that is sealed with pole piece injects electrolyte, then battery is placed on the jig of charging device, the positive pole of the corresponding lithium ion battery of anodal jig of charging device, the negative pole of the corresponding lithium ion battery of the negative pole jig of charging device, after setting charging current according to method of the present invention then battery is changed into, seal liquid injection hole then, the step of described sealing liquid injection hole can seal liquid injection hole after the charging process first time finishes the back and injects electrolyte once more in lithium rechargeable battery, carry out subsequent charging operations according to method of the present invention then, also can seal liquid injection hole again after finishing in the charging process second time.
To specify further the present invention by embodiment below.
Embodiment 1
This embodiment illustrates the preparation of lithium rechargeable battery.
(1) Zheng Ji preparation
The anodal active component LiFePO 4 of 100 grams, 2 gram binding agent polyvinylidene fluoride (PVDF), 3 gram conductive agent carbon blacks are mixed with 40 gram N-methyl pyrrolidones, in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on the aluminium foil equably, 150 ℃ of following oven dry, roll-ins then, cuts to make and be of a size of 540 * 43.5 millimeters positive pole, wherein contain 5.2 gram active component LiFePO 4 (LiFePO
4).
(2) preparation of negative pole
95 gram negative electrode active composition Delaniums, 5 gram binding agent polyvinylidene fluoride (PVDF) are mixed with 40 gram N-methyl pyrrolidones, in de-airing mixer, stir then and form uniform cathode size.
This slurry is coated on the Copper Foil equably, then in 90 ℃ of following oven dry, roll-in, cut to make and be of a size of 500 * 44 millimeters negative pole, wherein contain 2.6 gram active component Delaniums.
(3) assembling of battery and ageing
Above-mentioned positive and negative electrode and polypropylene screen are wound into the pole piece of a square lithium ion battery, lug and electrode slice point postwelding are put into battery container, after battery case and cover plate laser welded seal, LiPF
6Concentration by 1 mol is dissolved in EC/DMC=1: form nonaqueous electrolytic solution in 1 the mixed solvent, 2.5 these electrolyte of gram are injected battery case, in 45 ℃ hot environment, placed 24 hours, more even, fine and close to reach the purpose that electrolyte fully soaks into electrode active material in the electric core, to make the SEI film that forms in the formation process.Subsequently, prepare to change into.
The design capacity of the battery for preparing according to the method described above is 900 MAHs, and according to the amount of 3.9-4.1 gram/ampere-hour, total injection rate of the electrolyte of the battery of the present invention's preparation is about the 3.5-3.7 gram.
Embodiment 2
This embodiment illustrates the chemical synthesizing method of lithium rechargeable battery provided by the invention
Under normal pressure, 40 ℃, the battery that contains 2.5 gram electrolyte that earlier embodiment 1 is prepared is with the current charges to 3.4 of 0.05C volt, then under normal pressure, in described battery, re-inject electrolyte 1.2 grams, continuation with the electric current constant current charge to 3.8 of 1C volt, finishes changing under 40 ℃, and the sealing liquid injection hole, the model after obtaining changing into is 053450 rectangular lithium ion battery A1.
Embodiment 3
This embodiment illustrates the chemical synthesizing method of lithium rechargeable battery provided by the invention
Method according to embodiment 2 changes into the battery that contains 2.5 gram electrolyte that embodiment 1 prepares, different is, with behind the electric current constant current charge to 3.8 of 1C volt, under 45 ℃, battery placed to finish after 24 hours change into, and the sealing liquid injection hole, the model after obtaining changing into is 053450 rectangular lithium ion battery A2.
Embodiment 4
This embodiment illustrates the chemical synthesizing method of lithium rechargeable battery provided by the invention
The battery that contains 2.5 gram electrolyte that earlier embodiment 1 is prepared is with the current charges to 3.4 of 0.05C volt, and ageing was placed 12 hours under this temperature, (the yellow Hong Zhenkongshebeichang in Taizhou city produces to adopt vacuum pump then, model 2XCZ-04) battery is vacuumized, in vacuum degree is under 0.06 MPa, in described battery, re-inject electrolyte 1.2 grams, continuation is under 40 ℃, with the electric current constant current charge to 3.8 of 1C volt, and after ageing under this temperature is placed 24 hours, finish and change into, and the sealing liquid injection hole, the model after obtaining changing into is 053450 rectangular lithium ion battery A3.
Embodiment 5
This embodiment illustrates the chemical synthesizing method of lithium rechargeable battery provided by the invention
Method according to embodiment 1 prepares battery, and different is that in the assembling and aging step (3) of battery, the amount of the electrolyte that injects in battery container for the first time is 2.4 grams.
Then, with battery with the current charges to 3.4 of 0.05C volt, and ageing was placed 12 hours under this temperature, in described battery, re-inject electrolyte 1.3 grams then, continuation with behind the electric current constant current charge to 3.8 of 1C volt, is finished at 45 ℃ battery after placing 24 hours down changing into once more under 40 ℃, and the sealing liquid injection hole, the model after obtaining changing into is 053450 rectangular lithium ion battery A4.
Embodiment 6
This embodiment illustrates the chemical synthesizing method of lithium rechargeable battery provided by the invention
Method according to embodiment 5 changes into the battery that contains 2.4 gram electrolyte, different is, (the yellow Hong Zhenkongshebeichang in Taizhou city produces in order to adopt vacuum pump when injecting electrolyte for the second time, model 2XCZ-04) battery is vacuumized, in vacuum degree is to re-inject electrolyte 1.3 grams under 0.08 MPa in described battery, and other step and condition are with embodiment 5.Model after obtaining changing into is 053450 rectangular lithium ion battery A5.
Embodiment 7
This embodiment illustrates the chemical synthesizing method of lithium rechargeable battery provided by the invention
Method according to embodiment 1 prepares battery, and different is that in the assembling and aging step (3) of battery, the amount of the electrolyte that injects in battery container for the first time is 2.2 grams.
Under 50 ℃, the battery that earlier this is contained 2.2 gram electrolyte is with the current charges to 3.5 of 0.07C volt, and under 45 ℃, placed 12 hours, (the yellow Hong Zhenkongshebeichang in Taizhou city produces to adopt vacuum pump then, model 2XCZ-04) battery is vacuumized, making vacuum degree is under 0.08 MPa, in described battery, re-inject electrolyte 1.5 grams, and continue under 50 ℃, with the electric current constant current charge to 4.0 of 1C volt, after placing 24 hours under 45 ℃, finish changing into then, and the sealing liquid injection hole, the model after obtaining changing into is 053450 rectangular lithium ion battery A6.
Embodiment 8
This embodiment illustrates the chemical synthesizing method of lithium rechargeable battery provided by the invention
Method according to embodiment 1 prepares battery, and different is that in the assembling and aging step (3) of battery, the amount of the electrolyte that injects in battery container for the first time is 2.0 grams.
Under 55 ℃, the battery that earlier this is contained 2.0 gram electrolyte is with the current charges to 3.5 of 0.07C volt, and under 45 ℃, placed 12 hours, (the yellow Hong Zhenkongshebeichang in Taizhou city produces to adopt vacuum pump then, model 2XCZ-04) battery is vacuumized, in vacuum degree is under 0.08 MPa, in described battery, re-inject electrolyte 1.7 grams, and continue under 55 ℃, with the electric current constant current charge to 4.0 of 1C volt, after placing 24 hours under 45 ℃, finish changing into then, and the sealing liquid injection hole, the model after obtaining changing into is 053450 rectangular lithium ion battery A7.
Embodiment 9
This embodiment illustrates the chemical synthesizing method of lithium rechargeable battery provided by the invention
According to the method for embodiment 2 embodiment 1 is obtained battery and change into, different is that the described temperature that changes into is 25 ℃.Model after obtaining changing into is 053450 rectangular lithium ion battery A8.
Embodiment 10
This embodiment illustrates the chemical synthesizing method of lithium rechargeable battery provided by the invention
Method according to embodiment 1 prepares battery, and different is that in the assembling and aging step (3) of battery, the amount of the electrolyte that injects in battery container for the first time is 2.9 grams.
Under 40 ℃, the battery that contains 2.9 gram electrolyte that will prepare according to the method described above earlier is with the current charges to 3.4 of 0.05C volt, in described battery, re-inject electrolyte 0.8 gram (20%) then, continuation is under 40 ℃, with the electric current constant current charge to 3.8 of 1C volt, finish changing into, and the sealing liquid injection hole, the model after obtaining changing into is 053450 rectangular lithium ion battery A9.
Comparative Examples 1
The reference chemical synthesizing method of this Comparative Examples explanation lithium rechargeable battery
Method according to embodiment 1 prepares battery, and different is that in the assembling and aging step (3) of battery, the amount of the electrolyte that injects in battery container for the first time is 3.1 grams.
Under 25 ℃, battery with the current charges to 3.4 of 0.05C volt, is re-injected electrolyte 0.6 gram then in described battery, continuation is under 25 ℃, finish described formation process with behind the electric current constant current charge to 3.8 of 1C volt, and the sealing liquid injection hole, the reference cell AC1 after obtaining changing into.
Comparative Examples 2
The reference chemical synthesizing method of this Comparative Examples explanation lithium rechargeable battery
Method according to embodiment 1 prepares battery, and different is that in the assembling and aging step (3) of battery, the amount of the electrolyte that injects in battery container for the first time is 3.3 grams.
Under 25 ℃, battery with the current charges to 3.4 of 0.05C volt, is re-injected electrolyte 0.4 gram then in described battery, continuation is under 25 ℃, finish described formation process with behind the electric current constant current charge to 3.8 of 1C volt, and the sealing liquid injection hole, the reference cell AC2 after obtaining changing into.
Comparative Examples 3
The reference chemical synthesizing method of this Comparative Examples explanation lithium rechargeable battery
Method according to embodiment 1 prepares battery, and different is that in the assembling and aging step (3) of battery, the amount of the electrolyte that injects in battery container for the first time is 1.7 grams.
Under 25 ℃, battery with the current charges to 3.4 of 0.05C volt, is re-injected electrolyte 2.0 grams then in described battery, continuation is under 25 ℃, finish described formation process with behind the electric current constant current charge to 3.8 of 1C volt, and the sealing liquid injection hole, the reference cell AC3 after obtaining changing into.
Embodiment 11-20
The following example respectively to embodiment 2-10 obtain change into after lithium ion battery carry out performance test.
(1) cycle performance test
Under 25 ℃, the battery after will changing into according to the method for embodiment 2-10 then carries out the constant voltage charging with battery more respectively with 1C electric current constant current charge to 3.8 volt under this voltage, be 0.05C until cut-off current; After shelving 5 minutes, again with battery with 1C electric current constant-current discharge to 2.0 volt, the initial capacity of record battery, and repeat above step 1500 time, and the record battery is at 25 ℃, 1000 circulation backs are with the capacity of 1C current discharge to 2.0 volt, and the capacity sustainment rate of battery after the computation cycles according to the following equation, and measure the thickness of battery.The result is as shown in table 1.
Capacity sustainment rate (%)=(circulate 1000 times after battery capacity/battery initial capacity) * 100%
(2) multiplying power discharging property test
Battery is placed on test respectively cashier's office in a shop, earlier carry out constant current charge with the 0.2C electric current, charging to upper voltage limit is 3.6 volts, after shelving 10 minutes, electric current with 1C and 3C is discharged to 2.5 volts from 3.6 volts respectively, the ratio of the discharge capacity when writing down the discharge capacity of each battery and calculating respectively with the 0.2C discharge, that is:
C
1C/ C
0.2C: with the electric current of 1C from 3.6 volts be discharged to 2.5 volts discharge capacity with the electric current of 0.2C from 3.6 volts of ratios that are discharged to 2.5 volts discharge capacity;
C
3C/ C
0.2C: with the electric current of 3C from 3.6 volts be discharged to 2.5 volts discharge capacity with the electric current of 0.2C from 3.6 volts of ratios that are discharged to 2.5 volts discharge capacity.
The result is as shown in table 1.
Comparative Examples 4-6
Following Comparative Examples respectively to Comparative Examples 1-3 obtain change into after lithium ion battery carry out performance test.
Method according to embodiment 12-21 is carried out the test of capacity, cycle performance of battery and battery multiplying power discharging property to battery, and different is that the battery of test is the reference cell after the method for employing Comparative Examples 1-3 changes into.
The result is as shown in table 1.
Table 1
| The embodiment numbering | The battery numbering | Capacity sustainment rate (%) | C 1C/C 0.2CMultiplying power (%) | C 3C/C 0.2CMultiplying power (%) | Cell thickness (millimeter) |
| Embodiment 11 | A1 | 88.56 | 93.3 | 84.8 | 5.50 |
| Embodiment 12 | A2 | 89.95 | 94.2 | 86.2 | 5.48 |
| Embodiment 13 | A3 | 91.52 | 95.0 | 87.6 | 5.20 |
| Embodiment 14 | A4 | 85.98 | 93.1 | 84.2 | 5.50 |
| Embodiment 15 | A5 | 86.11 | 93.3 | 84.9 | 5.28 |
| Embodiment 16 | A6 | 84.59 | 91.6 | 82.4 | 5.33 |
| Embodiment 17 | A7 | 82.18 | 89.9 | 82.0 | 5.39 |
| Embodiment 18 | A8 | 80.19 | 88.0 | 80.0 | 5.47 |
| Embodiment 19 | A9 | 85.86 | 92.5 | 81.4 | 5.51 |
| Comparative Examples 4 | AC1 | 78.54 | 85.4 | 78.7 | 5.86 |
| Comparative Examples 5 | AC2 | 79.41 | 85.0 | 78.3 | 5.98 |
| Comparative Examples 6 | AC3 | 75.43 | 83.6 | 75.1 | 6.03 |
Data from last table 1 are after the lithium rechargeable battery of LiFePO 4 changes into to positive active material adopting method of the present invention as can be seen, battery after circulation 1000 times the capacity sustainment rate and the C of battery
1C/ C
0.2C, C
3C/ C
0.2CMultiplying power discharging property all obviously is better than adopting the reference cell after the method for Comparative Examples changes into, and the thickness of battery is also less than reference cell.Prove thus, the method that secondary fluid injection of the present invention, secondary change into not only can make the thickness of finished product battery be controlled effectively, can also make that organic electrolyte forms in the carbon negative terminal surface that one deck is complete, homogeneous, stable passivation layer SEI film, can effectively improve the capacity of battery, improve the cycle performance and the heavy-current discharge performance of battery, being specially adapted to the LiFePO 4 is the lithium rechargeable battery of positive active material.
Claims (8)
1, a kind of chemical synthesizing method of lithium rechargeable battery, this method comprises injects electrolyte in lithium rechargeable battery, changing under the temperature of lithium rechargeable battery battery is charged then, described charging method comprises charging process and charging process for the first time for the second time, in lithium rechargeable battery, inject electrolyte in the first time once more after the charging process, it is characterized in that, total amount with electrolyte that injects before the charging process first time and the electrolyte that injects after the charging process first time is a benchmark, the ratio of the electrolyte that injects before the charging process in the first time is 55 weight % to less than 70 weight %, and the ratio of the electrolyte of injection is greater than 30 weight % to 45 weight % after first time charging process; Described lithium rechargeable battery is that positive active material is the lithium rechargeable battery of LiFePO 4.
2, method according to claim 1, wherein, described first time, charging process comprised with first electric current constant current charge to the first voltage, described second time, charging process comprised with second electric current constant current charge to the second voltage, described second voltage is higher than first voltage, and described second electric current is more than or equal to first electric current.
3, method according to claim 2, wherein, described second voltage is higher than at least 0.1 volt of first voltage, and described second electric current is greater than first electric current 0.005C at least.
4, according to claim 2 or 3 described methods, wherein, described first electric current is 0.01-0.5C, and first voltage is the 3.0-3.5 volt; Described second electric current is 0.01-1.0C, and second voltage is the 3.5-4.0 volt.
5, method according to claim 1, wherein, this method is included in after the charging process first time, under vacuum condition, injects electrolyte in lithium rechargeable battery, and vacuum degree is the 0.06-0.1 MPa.
6, method according to claim 1, wherein, this method also is included in once more to be injected in lithium rechargeable battery after the electrolyte, the aging step before second time charging process, the temperature of described ageing is 30-80 ℃, and the time of ageing is 5-130 hour.
7, method according to claim 1, wherein, this method also is included in charging process aging step afterwards for the second time, and the temperature of described ageing is 30-80 ℃, and the time of ageing is 5-130 hour.
8, method according to claim 1, wherein, the temperature that changes into of described lithium rechargeable battery is 35-80 ℃.
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| WO2010081422A1 (en) * | 2009-01-15 | 2010-07-22 | 深圳市比克电池有限公司 | Pre-charging method for lithium-ion battery |
| KR101106359B1 (en) * | 2009-09-25 | 2012-01-18 | 삼성에스디아이 주식회사 | Method for manufacturing lithium ion secondary battery |
| CN102201563B (en) * | 2010-03-24 | 2016-02-10 | 深圳市比克电池有限公司 | Injection method of lithium ion battery electrolyte and the battery prepared |
| CN102035025A (en) * | 2010-08-23 | 2011-04-27 | 八叶(厦门)新能源科技有限公司 | Aging method of cylindrical lithium ion batteries |
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| CN111740168B (en) * | 2020-05-25 | 2021-06-22 | 宁波维科电池有限公司 | Method for manufacturing battery |
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