CN108400396A - A method of improving the first charge-discharge specific capacity of lithium ion battery and first effect - Google Patents
A method of improving the first charge-discharge specific capacity of lithium ion battery and first effect Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 71
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 230000000694 effects Effects 0.000 title claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000007600 charging Methods 0.000 claims abstract description 28
- 238000004064 recycling Methods 0.000 claims 1
- 230000010287 polarization Effects 0.000 description 14
- 230000008859 change Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000005611 electricity Effects 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000010278 pulse charging Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910005321 Li15Si4 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of first charge-discharge specific capacity improving lithium ion battery and the methods of first effect, include the following steps：A) by negative material with current density a1It is discharged to b1Voltage platform stands 20~40min, and it is multiple to recycle the process, stops this step cycle；B) successively with current density a2、a3……aiCarry out step A respectively) process stop electric discharge until a certain step or a certain stage discharge capacity≤0.1mAh；C) negative material for completing electric discharge is with current density A1Charge to B1Platform stands 20~40min, and it is multiple to recycle the process, stops this step cycle；D) successively with current density A2、A3……AjCarry out step C respectively) process stop charging until a certain step or charging capacity of a certain stage≤0.1mAh.The lithium ion battery that the application method obtains has higher coulombic efficiency for the first time and first charge-discharge capacity.
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of first charge-discharge ratios improving lithium ion battery
The method of capacity and first effect
Background technology
Lithium ion battery has many advantages, such as high power capacity, pollution-free, memory-less effect, is obtained in today's social life extensively
Using traditional negative electrode of lithium ion battery is made of graphite, and theoretical capacity is only 372mAh/g relatively low, negative what be there is now
In the material of pole, there are a graphite cathode material and silicium cathode material two major classes, graphite cathode has high-energy density, low-voltage, good
Conductivity, it is resourceful and cheap the advantages that, but graphite material is low there are charging capacity and surface is easy analysis lithium etc.
Disadvantage causes lithium ion battery available capacity relatively low and serious safety problem, with the development of social production, people are increasingly
The lithium ion battery for having high-energy density is needed, silicium cathode initially enters the visual field of people thus, and silicon is having high reason
By capacity (3587mAh/g, 9786mAh/cm3；Li15Si4) close to ten times of graphite cathode capacity, the reserves in nature most
Greatly, the advantages that environmentally safe.But silicium cathode has poor electric conductivity (＜ 10-3s/cm；25 DEG C) and carry out lithium from
Son is detached from and shows the volume change close to 300% when insertion.Huge volume change leads to the easy dusting of silicon particle, activity
Substance is poor with the contact of conductive agent/binder, solid electrolyte interface film repeated growth consumes the lithium source in electrolyte and anode,
In order to reduce side effect that volume expansion is brought and improve the electric conductivity of silicon materials, thus add in silicon materials graphite to
The silicon carbon material of formation.But even so still there is coulombic efficiency is low, first charge-discharge capacity is low for the first time etc. in silicon carbon material
Disadvantage.
For the first time coulombic efficiency and first charge-discharge capacity it is why important be all charging process generates because headed by voltage
Platform has established the basis of following cycle, and the size of coulombic efficiency characterizes the stability and dynamic performance of material structure for the first time
It is excellent whether, coulombic efficiency is low to mean that there are side reactions, it will directly reduce battery discharge capacity, shorten following for battery
In the ring service life, at the same time the charging capacity during following cycle is the fluctuation on the basis of the discharge capacity in first week.
Patent CN105186002A discloses a kind of method improving anode material for lithium-ion batteries discharge capacity, this method
Conductive agent is scattered in organic solvent and is ultrasonically treated, obtaining that treated, suspension is stirred for 20h, at the same time lithium
Ion battery positive active material gives dry-mixed under conditions of 170 DEG C~200 DEG C, then delays the suspension obtained by conductive agent
It is slow to be added in positive collection active material, it obtains powder and is ground finally to be calcined under the atmosphere of protective gas after dry.
This method step is relatively complicated, and cost is higher, and the period is longer.
Patent CN104795600A discloses a kind of method of raising lithium ion battery coulombic efficiency for the first time, include mainly with
Lower two steps, material modification are simultaneously subject to immersion treatment, and complex steps, cost is higher, and the period is longer.
Invention content
The purpose of the present invention is to provide a kind of first charge-discharge specific capacity improving lithium ion battery and the method for first effect,
Method in the present invention can effectively improve lithium ion battery coulombic efficiency and first charge-discharge capacity for the first time, and step is simple, at
This is low, and the period is short.
A kind of method that the present invention provides first charge-discharge specific capacity improving lithium ion battery and first effect, including following step
Suddenly：
A) by negative material with current density a1It is discharged to b1Voltage platform stands 20~40min, it is several to recycle the process
It is secondary, stop this step cycle；
B) successively with current density a2、a3……aiCarry out step A respectively) process, until a certain step or a certain stage
Specific discharge capacity≤0.1mAh/g stops electric discharge；
C) negative material for completing electric discharge is with current density A1Charge to B1Platform stands 20~40min, recycles the mistake
Journey several times, stops this step cycle；
D) successively with current density A2、A3……AjCarry out step C respectively) process, until a certain step or a certain stage
Charging capacity≤0.1mAh/g stops charging；
Wherein, 0.05C≤ai≤1C；0.001V≤b1≤0.01V；0.05C≤Aj≤1C；1.5V≤B1≤2V；i≥3；j
≥3。
Preferably, in each independent stage, each stage with current constant mode by battery charge or discharge to predetermined
End after voltage value.
Preferably, a1≥a2≥a3、……≥ai。
Preferably, the A1≥A2≥A3、……≥Aj。
Preferably, 0.005V≤b1≤0.006V。
Preferably, by negative material with current density a1It is discharged to b1Voltage platform stands 20~40min, repeats 2~5
It is secondary；
With current density a2It is discharged to b2Voltage platform stands 20~40min, repeats 2~5 times；
With current density a3It is discharged to b3Voltage platform stands 20~40min, repeats 2~5 times；
With current density a4It is discharged to b4Voltage platform stands 20~40min, is repeated up to a certain step or a certain stage
Specific discharge capacity≤0.1mAh/g；
0.8C≤a1≤1C；0.5C≤a2≤0.7C；0.1C≤a3≤0.4C；0.05C≤a4≤0.08C.Wherein C is should
The theoretical specific capacity of negative material.
Preferably, by negative material with current density A1Charge to B1Voltage platform stands 20~40min, repeats 2~5
It is secondary；
With current density A2Charge to B2Voltage platform stands 20~40min, repeats 2~5 times；
With current density A3Charge to B3Voltage platform stands 20~40min, repeats 2~10 times；
With current density A4Charge to B4Voltage platform stands 20~40min, is repeated up to a certain step or a certain stage
Specific discharge capacity≤0.1mAh/g；
0.8C≤A1≤1C；0.5C≤A2≤0.7C；0.1C≤A3≤0.4C；0.05C≤A4≤0.08C.Wherein, C is to be somebody's turn to do
The theoretical specific capacity of negative material.
The present invention provides a kind of first charge-discharge specific capacity improving lithium ion battery and the method for first effect, including it is following
Step：A) by negative material with current density a1It is discharged to b1Voltage platform stands 20~40min, and it is multiple to recycle the process, stops
Only this step cycle；B) successively with current density a2、a3……aiRespectively carry out step A) process, until a certain step or certain
One stage discharge capacity≤0.1mAh stops electric discharge；C) negative material for completing electric discharge is with current density A1Charge to B1It is flat
Platform stands 20~40min, and it is multiple to recycle the process, stops this step cycle；D) successively with current density A2、A3……AjRespectively
Carry out step C) process stop charging until a certain step or charging capacity of a certain stage≤0.1mAh；Wherein, 0.05C≤
ai≤1C；0.001V≤b1≤0.01V；0.05C≤Aj≤1C；1.5V≤B1≤2V；i≥3；j≥3.
For lithium ion battery when being discharged with a certain constant current density, standing can find voltage than default electricity after a certain period of time
Pressure value wants high, and when being charged with a certain constant current density, standing can find that voltage is lower than preset voltage value, says after a certain period of time
The polarization phenomena of bright inside battery are more serious, and (battery is in charge and discharge process since polarization, electrode potential deviate from flat
Weigh electrode potential, and after shelving, polarization is slowly eliminated, so electrode potential is varied from, causes the change of cell voltage
Change).
The charge and discharge algorithm for the pulsed that the present invention uses can weaken electricity for disposable charge and discharge algorithm
Polarization inside pond makes battery lithium ion in charge and discharge process be embedded in more thorough with abjection.Lithium-ion electric can be eliminated
Ohmic polarization inside pond reduces internal resistance, effectively slows down voltage in battery and increases, makes battery in next charging process
It can receive more electricity.In addition to this it can also extend the service life of battery, reduce the charging time, improve active material
Utilization rate, the advantages that forming preferable SEI films.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the detailed process parameter of pulse charging in the embodiment of the present invention 1；
Fig. 2 is the detailed process parameter of pulsed discharge in the embodiment of the present invention 1；
Fig. 3 is the voltage change curve during 1 pulsed discharge of the embodiment of the present invention；
Fig. 4 is the voltage change curve during 1 pulse charging of the embodiment of the present invention；
Fig. 5 is the detailed process parameter of 1 constant current mode charge and discharge of comparative example of the present invention；
Fig. 6 is the voltage change curve in 1 constant current mode discharge process of comparative example of the present invention；
Fig. 7 is the voltage change curve in 1 constant current mode charging process of comparative example of the present invention.
Specific implementation mode
The present invention provides a kind of first charge-discharge specific capacity improving lithium ion battery and the method for first effect, including it is following
Step：
A negative material) is stood into 20~40min, with current density a1It is discharged to b1Voltage platform, it is multiple to recycle the process,
Stop this step cycle；
B) successively with current density a2、a3……aiCarry out step A respectively) process, until a certain step or a certain stage
Discharge capacity≤0.1mAh stops electric discharge；
C) negative material for completing electric discharge stands 20~40min, with current density A1Charge to B1Platform recycles the mistake
Cheng Duoci stops this step cycle；
D) successively with current density A2、A3……AjCarry out step C respectively) process, until a certain step or a certain stage
Charging capacity≤0.1mAh stops charging；
Wherein, 0.05C≤ai≤1C；0.001V≤b1≤0.01V；0.05C≤Aj≤1C；1.5V≤B1≤2V；i≥3；j
≥3。
Lithium ion battery in the present invention in a pulsed fashion charges and discharges negative material, and with high current
Density is charged and discharged contributes to the capacity for further playing its charge and discharge, together for starting with low current density electric discharge to end
When the process of single phase constant current charge-discharge is repeated as many times again, its voltage drop can be reduced, realize that further charge and discharge are deep
Degree macro manifestations are improved for charge/discharge capacity, and in addition to this, process repeatedly can form preferable SEI films.
The present invention is by negative material with current density a1It is discharged to b1Voltage platform stands 20~40min, preferably
30min；It repeats 1~2 time；0.8C≤a1≤1C；Preferably 1C；
With current density a2It is discharged to b1Voltage platform stands 20~40min, preferably 30min；It repeats 3~5 times；0.5C
≤a2≤0.7C；Preferably 0.5C；
With current density a3It is discharged to b1Voltage platform stands 20~40min, preferably 30min；It repeats 6~12 times；
0.1C≤a3≤0.4C；Preferably 0.1C；
With current density a4It is discharged to b1Voltage platform stands 20~40min, preferably 30min；It is repeated up to a certain step
Rapid or a certain stage discharge specific capacity≤0.1mAh；0.05C≤a4≤0.08C；Preferably 0.05C.
Wherein, negative material is preferably silicon-carbon cathode material；0.001V≤b1≤ 0.01V, preferably 0.005V≤b1≤
0.006V。
There are two the criterions that the present invention stops discharge process, and one is with constant current aiThe specific capacity of electric discharge
≤ 0.1mAh/g can stop discharge step, carry out subsequent charge step；Second standard is when with constant current aiElectric discharge
After, find the voltage difference after its voltage and the stage discharge in 0.01V or less after standing 30min or so time
When, you can stop electric discharge.
Above-mentioned two standards with first specific capacity be main judgment basis, while should refer to Article 2 standard, with save
Corresponding discharge time.
After the completion of electric discharge, the present invention continues negative material to charge according to the following steps：
By negative material with current density A1Charge to B1Voltage platform stands 20~40min, preferably 30min；Repeat 1
~2 times；0.8C≤A1≤1C；Preferably 1C；
With current density A2Charge to B1Voltage platform stands 20~40min, preferably 30min；It repeats 3~5 times；0.5C
≤A2≤0.7C；Preferably 0.5C；
With current density A3Charge to B1Voltage platform stands 20~40min, preferably 30min；It repeats 6~12 times；
0.1C≤A3≤0.4C；Preferably 0.1C；
With current density A4Charge to B1Voltage platform stands 20~40min, preferably 30min；It is repeated up to a certain step
Rapid or a certain stage discharge capacity≤0.1mAh/g；0.05C≤A4≤ 0.08C, preferably 0.05C.
Wherein, 1.5V≤B1≤2V；Preferably 1.8V≤B1≤2V
There are two the criterions that the present invention stops charging process, and one is with constant current aiThe specific capacity of charging
≤ 0.1mAh/g can stop charge step；Second standard is when with constant current aiAfter charging, it is left to stand 30min
Find the voltage difference after its voltage charges with the stage in 0.01V or less after the right time, you can to stop charging.
Above-mentioned two standards with first specific capacity be main judgment basis, while should refer to Article 2 standard, with save
The corresponding charging time.
The present invention provides a kind of first charge-discharge specific capacity improving lithium ion battery and the method for first effect, including it is following
Step：A negative material) is stood into 20~40min, with current density a1It is discharged to b1Voltage platform, it is multiple to recycle the process, stops
Only this step cycle；B) successively with current density a2、a3……aiRespectively carry out step A) process, until a certain step or certain
One stage discharge capacity≤0.1mAh stops electric discharge；C) negative material for completing electric discharge stands 20~40min, close with electric current
Spend A1Charge to B1Platform, it is multiple to recycle the process, stops this step cycle；D) successively with current density A2、A3……AjRespectively
Carry out step C) process stop charging until a certain step or charging capacity of a certain stage≤0.1mAh；Wherein, 0.05C≤
ai≤1C；0.001V≤b1≤0.01V；0.05C≤Aj≤1C；1.5V≤B1≤2V；i≥3；j≥3.
For lithium ion battery when being discharged with a certain constant current density, standing can find voltage than default electricity after a certain period of time
Pressure value wants high, and when being charged with a certain constant current density, standing can find that voltage is lower than preset voltage value, says after a certain period of time
The polarization phenomena of bright inside battery are more serious, and (battery is in charge and discharge process since polarization, electrode potential deviate from flat
Weigh electrode potential, and after shelving, polarization is slowly eliminated, so electrode potential is varied from, causes the change of cell voltage
Change).
The charge and discharge algorithm for the pulsed that the present invention uses can weaken electricity for disposable charge and discharge algorithm
Polarization inside pond makes battery lithium ion in charge and discharge process be embedded in more thorough with abjection.Lithium-ion electric can be eliminated
Ohmic polarization inside pond reduces internal resistance, effectively slows down voltage in battery and increases, makes battery in next charging process
It can receive more electricity.In addition to this it can also extend the service life of battery, reduce the charging time, improve active material
Utilization rate, the advantages that forming preferable SEI films.
In order to further illustrate the present invention, a kind of lithium ion battery is improved to provided by the invention with reference to embodiments
The method of first charge-discharge specific capacity and first effect is described in detail, but cannot be understood as the limit to the scope of the present invention
It is fixed.
Embodiment 1
By taking fastening lithium ionic cell as an example, negative material is silicon-carbon cathode material；Conductive agent is electrically conductive graphite
Specific discharge process as shown in FIG. 1, FIG. 1 is the detailed process discharged in the embodiment of the present invention 1, due to process compared with
It is long, interception electric discharge start-up portion and electric discharge latter end, intermediate omission processing.In Fig. 1,
1st~2 week cycle is that 1C current densities charge to 0.005V, and the 3rd~5 week cycle is that 0.5C current densities are discharged to
0.005V is discharged to 0.005V on the 6th~12 week for 0.1C current densities, and cycles left is that 0.05C current densities are discharged to
0.005V；Until a certain step or a certain stage discharge specific capacity≤0.1mAh/g；
Specific charging process is as shown in Fig. 2, Fig. 2 is the detailed process to charge in the embodiment of the present invention 1, in Fig. 2,
1st~2 week cycle is that 1C current densities charge to 2V, and the 3rd~5 week cycle is that 0.5C current densities charge to 2V,
2V is charged to for 0.1C current densities within 6th~12 week, cycles left is that 0.05C current densities charge to 2V；Until a certain step
Or a certain stage charge specific capacity≤0.1mAh/g；
Initial charge specific capacity is 444.3mAh/g in the present embodiment it can be seen from Fig. 1 and Fig. 2, and discharge specific volume for the first time
Amount is 525.6mAh/g, and coulombic efficiency is 84.5% for the first time.
Embodiment 2~4
First circle charge and discharge are carried out according to the method button type lithium ion battery in embodiment 1.Unlike, embodiment 2~4
In conductive agent be followed successively by electrically conductive graphite and conductive carbon black mass ratio 1:1 mixture, graphene and conductive carbon black.
Comparative example 1~4
The fastening lithium ionic cell in Examples 1 to 4 is respectively adopted, 0.005V is discharged to using the current density of 0.15C,
After standing 2min, carries out charging to 2V using the current density of 0.15C, complete first circle charge and discharge.
The coulombic efficiency for the first time of Examples 1 to 4 and comparative example 1~4 and discharge capacity is as shown in table 1 for the first time,
The coulombic efficiency for the first time of 1 embodiment of the present invention 1~4 of table and comparative example 1~4 and for the first time discharge capacity
As shown in figure 3 to figure 7, Fig. 3 is arteries and veins to the charging/discharging voltage curve of embodiment 1 and comparative example 1 it can be seen from Fig. 3~7
Rush the real-time voltage curve in formula discharge process, due to the discharge process of pulsed be when with a certain current density by cell voltage
When being put into given voltage, since there are certain polarization phenomena for inside battery, (battery is in charge and discharge process since polarization is made
With, electrode potential deviates from equilibrium electrod potential, and after shelving, polarization is slowly eliminated, so electrode potential is varied from,
Cause the variation of cell voltage.)
So will appear the case where voltage rises after standing a period of time, we are discharged using more processes thus, Zhi Dao electricity
Until when pond internal polarization phenomenon is weaker, so the case where real-time voltage curve will appear rise and fall repeatedly, conversely, charging
It will appear the case where cell voltage declines after standing a period of time in journey.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of method of first charge-discharge specific capacity improving lithium ion battery and first effect, includes the following steps：
A) by negative material with current density a1It is discharged to b1Voltage platform stands 20~40min, recycles the process several times, stop
Only this step cycle；
B) successively with current density a2、a3……aiCarry out step A respectively) process, until a certain step or a certain stage discharge
Specific capacity≤0.1mAh/g stops electric discharge；
C) negative material for completing electric discharge is with current density A1Charge to B1Platform stands 20~40min, if recycling the process
Dry time, stop this step cycle；
D) successively with current density A2、A3……AjCarry out step C respectively) process, until a certain step or a certain stage charge
Specific capacity≤0.1mAh/g stops charging；
Wherein, 0.05C≤ai≤1C；0.001V≤b1≤0.01V；0.05C≤Aj≤1C；1.5V≤B1≤2V；i≥3；j≥3；
Wherein, C is the theoretical specific capacity of the negative material.
2. according to the method described in claim 1, it is characterized in that, in each independent stage, each stage is with constant current
Mode will end after battery charge or discharge to scheduled voltage.
3. according to the method described in claim 1, it is characterized in that, a1≥a2≥a3、……≥ai。
4. according to the method described in claim 1, it is characterized in that, the A1≥A2≥A3、……≥Aj。
5. according to the method described in claim 1, it is characterized in that, 0.005V≤b1≤0.006V。
6. according to the method described in claim 1, it is characterized in that, by negative material with current density a1It is discharged to b1Voltage is flat
Platform stands 20~40min, repeats 2~5 times；
With current density a2It is discharged to b2Voltage platform stands 20~40min, repeats 2~5 times；
With current density a3It is discharged to b3Voltage platform stands 20~40min, repeats 2~5 times；
With current density a4It is discharged to b4Voltage platform stands 20~40min, is repeated up to a certain step or a certain stage discharge
Specific capacity≤0.1mAh/g；
0.8C≤a1≤1C；0.5C≤a2≤0.7C；0.1C≤a3≤0.4C；0.05C≤a4≤0.08C；Wherein, C is the cathode
The theoretical specific capacity of material.
7. according to the method described in claim 1, it is characterized in that, by negative material with current density A1Charge to B1Voltage is flat
Platform stands 20~40min, repeats 2~5 times；
With current density A2Charge to B2Voltage platform stands 20~40min, repeats 2~5 times；
With current density A3Charge to B3Voltage platform stands 20~40min, repeats 2~10 times；
With current density A4Charge to B4Voltage platform stands 20~40min, is repeated up to a certain step or a certain stage discharge
Specific capacity≤0.1mAh/g；
0.8C≤A1≤1C；0.5C≤A2≤0.7C；0.1C≤A3≤0.4C；0.05C≤A4≤0.08C；Wherein, C is the cathode
The theoretical specific capacity of material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111811905A (en) * | 2020-07-24 | 2020-10-23 | 天津市捷威动力工业有限公司 | Electrochemical matching rapid evaluation method |
| CN116430257A (en) * | 2023-06-15 | 2023-07-14 | 四川新能源汽车创新中心有限公司 | Method for representing electrical performance of lithium battery and application thereof |
| CN117117358A (en) * | 2023-02-25 | 2023-11-24 | 荣耀终端有限公司 | Battery processing method and battery |
| CN118409235A (en) * | 2024-07-03 | 2024-07-30 | 宁德时代新能源科技股份有限公司 | Battery safety detection method, device, electronic equipment and storage medium |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102097656A (en) * | 2010-12-19 | 2011-06-15 | 重庆戴徕密客电源有限公司 | Method for forming high-capacity lithium iron phosphate lithium ion battery |
| CN103326069A (en) * | 2012-03-20 | 2013-09-25 | 北汽福田汽车股份有限公司 | Method for forming lithium manganese power cells |
| CN104037456A (en) * | 2014-06-16 | 2014-09-10 | 张晶晶 | Rapid forming process of iron phosphate lithium battery |
| CN107039700A (en) * | 2016-08-22 | 2017-08-11 | 杜文龙 | A kind of old dynamic lithium battery improves the multistep chemical synthesizing method of Capacity uniformity |
-
2018
- 2018-03-07 CN CN201810187262.1A patent/CN108400396B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102097656A (en) * | 2010-12-19 | 2011-06-15 | 重庆戴徕密客电源有限公司 | Method for forming high-capacity lithium iron phosphate lithium ion battery |
| CN103326069A (en) * | 2012-03-20 | 2013-09-25 | 北汽福田汽车股份有限公司 | Method for forming lithium manganese power cells |
| CN104037456A (en) * | 2014-06-16 | 2014-09-10 | 张晶晶 | Rapid forming process of iron phosphate lithium battery |
| CN107039700A (en) * | 2016-08-22 | 2017-08-11 | 杜文龙 | A kind of old dynamic lithium battery improves the multistep chemical synthesizing method of Capacity uniformity |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111811905A (en) * | 2020-07-24 | 2020-10-23 | 天津市捷威动力工业有限公司 | Electrochemical matching rapid evaluation method |
| CN117117358A (en) * | 2023-02-25 | 2023-11-24 | 荣耀终端有限公司 | Battery processing method and battery |
| CN116430257A (en) * | 2023-06-15 | 2023-07-14 | 四川新能源汽车创新中心有限公司 | Method for representing electrical performance of lithium battery and application thereof |
| CN116430257B (en) * | 2023-06-15 | 2023-09-19 | 四川新能源汽车创新中心有限公司 | Method for representing electrical performance of lithium battery and application thereof |
| CN118409235A (en) * | 2024-07-03 | 2024-07-30 | 宁德时代新能源科技股份有限公司 | Battery safety detection method, device, electronic equipment and storage medium |
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