CN108931736A - A kind of determination method of lithium ion battery analysis lithium critical condition - Google Patents
A kind of determination method of lithium ion battery analysis lithium critical condition Download PDFInfo
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- CN108931736A CN108931736A CN201810769863.3A CN201810769863A CN108931736A CN 108931736 A CN108931736 A CN 108931736A CN 201810769863 A CN201810769863 A CN 201810769863A CN 108931736 A CN108931736 A CN 108931736A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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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Abstract
The present invention provides a kind of determination methods of lithium ion battery analysis lithium critical condition, comprising: S1) at the same temperature, it is charged using different rate of charge to lithium ion battery, records anode potential；S2) according to anode potential and charging current or the relationship of rate of charge, obtain lithium ion battery critical analysis lithium electric current or critical analysis lithium multiplying power.Compared with prior art, determination method provided by the invention quantitatively can analyse the critical multiplying power or electric current of lithium by anticipation lithium ion battery, and not have to dismantling battery, time saving and energy saving, economize on resources, accuracy is high.
Description
Technical field
The invention belongs to the judgements of technical field of lithium ion more particularly to a kind of lithium ion battery analysis lithium critical condition
Method.
Background technique
Lithium ion battery is as new green energy, in recent years by common concern, but as its application space is constantly expanded
Greatly, market is also more harsh to its demand, especially applies the lithium ion battery in electric vehicle now, is faced with two disasters
Point, big multiplying power charging performance and low temperature charging performance.
When low temperature or big multiplying power charge, inside battery polarization can be all caused to increase, anode overpotential is larger, the lithium in battery core
Ion is precipitated in anode surface, not can guarantee so as to cause its security performance, therefore judges that the critical of analysis lithium occurs for battery core in advance
Condition is particularly important.
Currently, most common method be by battery different multiplying and at a temperature of charge, then disassemble battery, naked eyes judge
Whether lithium ion battery analyses lithium and analysis lithium degree.But such method can only qualitatively judge, and expend a large amount of manpower and material resources, in battery
There are also certain security risks for dismantling process.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of determining for lithium ion battery analysis lithium critical condition
Amount determination operation.
The present invention provides a kind of determination methods of lithium ion battery analysis lithium critical condition, comprising:
S1) at the same temperature, charged using different rate of charge to lithium ion battery, record anode potential；
S2) according to anode potential and charging current or the relationship of rate of charge, the critical analysis lithium electricity of lithium ion battery is obtained
Stream or critical analysis lithium multiplying power.
Preferably, the step S2) specifically: according to the anode potential of record, establish anode potential and charging current or
The fit equation of rate of charge, obtains the area Xi Li fit equation and the area Fei Xili fit equation, and the crosspoint of two equations is lithium
The critical analysis lithium electric current of ion battery or critical analysis lithium multiplying power.
Preferably, the temperature is 5 DEG C~30 DEG C.
Preferably, the rate of charge is 0.1~3C.
Preferably, the lithium ion battery is to plate lithium electrode as reference electrode.
Preferably, the S1) in when lithium ion battery changes locating temperature condition, stand 30~240min, then
It is charged again using different rate of charge.
Preferably, the step S1) in using different rate of charge to lithium ion battery charge when, every time charging terminate
Afterwards, 1~10min is stood, anode potential is recorded, after then being discharged, stands 1~10min, then charged next time.
Preferably, the electric discharge uses 1C electric current.
The present invention provides a kind of determination methods of lithium ion battery analysis lithium critical condition, comprising: S1) in same temperature
Under, it is charged using different rate of charge to lithium ion battery, records anode potential；S2) according to anode potential and charging current
Or the relationship of rate of charge, obtain lithium ion battery critical analysis lithium electric current or critical analysis lithium multiplying power.Compared with prior art, originally
Inventing the determination method provided quantitatively can analyse the critical multiplying power or electric current of lithium by anticipation lithium ion battery, and not have to dismantling battery, save
Shi Shengli economizes on resources, and accuracy is high.
Detailed description of the invention
When Fig. 1 is that charging current is 4A in comparative example 1 of the present invention, the photo at battery core interface；
When Fig. 2 is that charging current is 4.5A in comparative example 1 of the present invention, the photo at battery core interface；
When Fig. 3 is that charging current is 1.67A in comparative example 2 of the present invention, the photo at battery core interface；
When Fig. 4 is that charging current is 2A in comparative example 2 of the present invention, the photo at battery core interface；
When Fig. 5 is that charging current is 3.89A in comparative example 3 of the present invention, the photo at battery core interface；
When Fig. 6 is that charging current is 4.5A in comparative example 3 of the present invention, the photo at battery core interface.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of determination methods of lithium ion battery analysis lithium critical condition, comprising: S1) in same temperature
Under, it is charged using different rate of charge to lithium ion battery, records anode potential；S2 it) according to the anode potential of record, establishes
The fit equation of anode potential and charging current or rate of charge, obtains the critical analysis lithium electric current or critical analysis lithium of lithium ion battery
Multiplying power.
The present invention is not particularly limited the source of all raw materials, is commercially available.
At the same temperature, it is charged using different rate of charge to lithium ion battery, records anode potential；Wherein, institute
Stating temperature is preferably 5 DEG C~30 DEG C, more preferably 10 DEG C~25 DEG C；The lithium ion battery is well known to those skilled in the art
Lithium ion battery, has no special limitation, preferably to plate lithium electrode as reference electrode in the present invention；When lithium ion battery changes
When becoming locating temperature condition, 30~240min, more preferably 60~200min are preferably first stood, further preferably for 100~
180min, most preferably 120~140min, then charged using different rate of charge；To ensure each charge condition one
Sample after preferably first being discharged, then uses different rate of charge to charge；The electric discharge is preferably carried out using 1C electric current；
The electric discharge is preferably discharged to low cutoff voltage；The rate of charge is preferably 0.1~3C；The charging preferably charges to
Limit blanking voltage；Every time charging after, preferably standing 1~10min, more preferably standing 4~8min, further preferably stand 5~
6min records anode potential, after then being discharged, then is charged next time；The electric discharge is preferably carried out using 1C electric current.
According to anode potential and charging current or the relationship of rate of charge, obtain lithium ion battery critical analysis lithium electric current or
Critical analysis lithium multiplying power.This step in the present invention specifically: according to the anode potential of record, establish anode potential and charging current
Or the fit equation of rate of charge voltage and rate of charge or is filled since battery analysis lithium is different from lithium anode surface state is not analysed
Electric current shows different mechanism, obtains different fit equations, by taking electric current as an example, the area Fei Xili fit equation U1=k1*I+b1
(k1For slope, b1For intercept), the area Xi Li: U2=k2*I+b2(k2For slope, b2For intercept), the crosspoint of two equations is lithium
The critical analysis lithium electric current of ion battery or critical analysis lithium multiplying power obtain under experimental temperature according to above-mentioned equation solution equation group
Critical analysis lithium electric current or multiplying power.
Determination method provided by the invention quantitatively can analyse the critical multiplying power or electric current of lithium by anticipation lithium ion battery, and not have to tear open
Electrolytic cell, it is time saving and energy saving, it economizes on resources, accuracy is high.
In order to further illustrate the present invention, a kind of lithium ion battery analysis lithium provided by the invention is faced with reference to embodiments
The quantitative judgement method of boundary's condition is described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
Battery uses ternary material: NCM523；Anode material: (gram volume plays 340mAh/g, degree of graphitization to graphite AK01
94%)；Electrolyte with the lithium hexafluoro phosphate (LiPF6) of concentration 1.0M be lithium salts, using vinylene carbonate as additive, with carbonic acid
The mixture of acrylic ester (PC), ethylene carbonate (EC) and dimethyl carbonate (DMC) is made for solvent；Lithium ion battery is measured to exist
Different multiplying charge when rated condition under anode to lithium current potential Ux。
Embodiment is specifically described as follows:
Battery core is embedded to copper wire in preparatory phase, handles after battery core activation copper wire plating lithium and reference electrode is made；Subsequent battery core
Merging high-low temperature chamber simultaneously accesses charge and discharge cabinet, completes to test by process, collects data.
Specific testing process is as follows:
1) adjustment environment temperature is T (T is the setting of experiment demand)；
2) 120min is stood；
3) nominal 1C current discharge is to low cutoff voltage；
4) 5min is stood；
5) nominal XC electric current charges to upper limit blanking voltage (X 0.1,0.5,1,1.5,2,3)；
6) 5min is stood.
Record same temperature, under different multiplying, the corresponding current potential U of anodex。
By test data, lithium ion battery charging process anode potential Ux and charging current I equation are established, due to battery
Analysis lithium is different from lithium anode surface state is not analysed, and current potential Ux shows different mechanism from charging current I, obtains different fitting sides
Journey；
The area Fei Xili: U1=k1*I+b1(k1For slope, b1For intercept)
The area Xi Li: U2=k2*I+b2(k2For slope, b2For intercept)
The critical analysis lithium electric current under the conditions of experimental temperature, 25 DEG C of lower criticals are obtained by the equation solution equation group that fitting obtains
Analysis lithium charging current is 4.03A, and 10 DEG C of lower critical analysis lithium charging currents are 1.67A.
Ux under 1 25 DEG C of table different electric currents
| I/A | 0.229 | 1.145 | 2.290 | 3.435 | 4.580 | 5.725 | 6.870 |
| Ux current potential/V | 0.0464 | 0.0224 | -0.0033 | -0.0281 | -0.0479 | -0.0637 | -0.0724 |
Fit equation U1=-0.0231*I+0.0504；
Fit equation U2=-0.0107*I-0.0001；
Ux under 2 10 DEG C of table different electric currents
| I/A | 0.229 | 0.570 | 0.921 | 1.141 | 2.290 | 3.440 | 3.580 |
| Ux current potential/V | 0.0280 | 0.0121 | -0.0027 | -0.0118 | -0.0541 | -0.0717 | -0.0907 |
Fit equation U1=-0.0516*I+0.0378；
Fit equation U2=-0.0143*I+0.0294；
Embodiment 2
Battery uses ternary material: NCM523；Anode material: (gram volume plays 350mAh/g, graphite to artificial graphite SF01
Change degree 96.5%)；Electrolyte with the lithium hexafluoro phosphate (LiPF6) of concentration 1.0M be lithium salts, using vinylene carbonate as additive,
It is made by solvent of the mixture of propene carbonate (PC), ethylene carbonate (EC) and dimethyl carbonate (DMC).
Using the method for embodiment 1 measure lithium ion battery when 25 DEG C of different multiplyings charge anode to lithium current potential Ux, sentence
The critical analysis lithium electric current that breaks is 3.89A.
Ux under 3 25 DEG C of table different electric currents
| I/A | 0.229 | 1.145 | 2.290 | 3.435 | 4.580 | 5.725 | 6.870 |
| Ux current potential/V | 0.0352 | 0.0102 | -0.0150 | -0.0394 | -0.0557 | -0.0664 | -0.0727 |
Fit equation U1=-0.0231*I+0.0387；
Fit equation U2=-0.0074*I-0.0224；
Comparative example 1
Using the lithium ion battery in embodiment 1,25 DEG C of temperature (room temperature) is controlled, is first charged under different multiplying, then
It disassembles full charge core and observing interface analysis lithium situation by hand in safe house, judges critical analysis lithium multiplying power；Wherein Fig. 1 is charging electricity
When stream is 4A, the photo at battery core interface, no analysis lithium phenomenon, Fig. 2 is charging current when being 4.5A, the photo at battery core interface,
There is slight analysis lithium；By the critical analysis lithium electric current of room temperature of Fig. 1 and Fig. 2 deducibility this lithium ion battery between 4~4.5A.
Comparative example 2
Using the lithium ion battery in embodiment 1,10 DEG C of temperature are controlled, is first charged under different multiplying, then in safety
Full charge core and observing interface analysis lithium situation are disassembled in room by hand, judges critical analysis lithium multiplying power；Wherein Fig. 3 is that charging current is
When 1.67A, the photo at battery core interface, no analysis lithium phenomenon, Fig. 4 is charging current when being 2A, the photo at battery core interface, has light
Micro- analysis lithium；By 10 DEG C of critical analysis lithium electric currents of Fig. 3 and Fig. 4 deducibility this lithium ion battery between 1.67~2A.
Comparative example 3
Using the lithium ion battery in embodiment 2,25 DEG C of temperature (room temperature) is controlled, is first charged under different multiplying, then
It disassembles full charge core and observing interface analysis lithium situation by hand in safe house, judges critical analysis lithium multiplying power；Wherein Fig. 5 is charging electricity
When stream is 3.89A, the photo at battery core interface, no analysis lithium phenomenon, Fig. 6 is charging current when being 4.5A, the photo at battery core interface,
It has slight analysis lithium；By the critical analysis lithium electric current of room temperature of Fig. 5 Yu Fig. 6 deducibility this lithium ion battery in 4A or so.
Claims (8)
1. a kind of determination method of lithium ion battery analysis lithium critical condition characterized by comprising
S1) at the same temperature, charged using different rate of charge to lithium ion battery, record anode potential；
S2) according to anode potential and charging current or the relationship of rate of charge, obtain lithium ion battery critical analysis lithium electric current or
Critical analysis lithium multiplying power.
2. determination method according to claim 1, which is characterized in that the step S2) specifically: according to the anode of record
Current potential establishes the fit equation of anode potential and charging current or rate of charge, obtains the area Xi Li fit equation and the area Fei Xili
Fit equation, critical analysis lithium electric current or critical analysis lithium multiplying power of the crosspoint of two equations for lithium ion battery.
3. determination method according to claim 1, which is characterized in that the temperature is 5 DEG C~30 DEG C.
4. determination method according to claim 1, which is characterized in that the rate of charge is 0.1~3C.
5. determination method according to claim 1, which is characterized in that the lithium ion battery is to plate lithium electrode as reference electricity
Pole.
6. determination method according to claim 1, which is characterized in that the S1) in when lithium ion battery change it is locating
When temperature condition, 30~240min is stood, is then charged again using different rate of charge.
7. determination method according to claim 1, which is characterized in that the step S1) it is middle using different rate of charge
When to lithium ion battery charging, every time after charging, 1~10min is stood, records anode potential, it is quiet after then being discharged
1~10min is set, then is charged next time.
8. determination method according to claim 7, which is characterized in that the electric discharge uses 1C electric current.
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Effective date of registration: 20220117 Address after: 215500 room 808, No. 1, Southeast Avenue, Changshu high tech Industrial Development Zone, Changshu, Suzhou, Jiangsu Patentee after: Jiangsu Zhengli new energy battery technology Co.,Ltd. Address before: 211100 Lantian Road 249, Airport Economic Development Zone, Jiangning District, Nanjing City, Jiangsu Province Patentee before: JIANGSU TAFEL NEW ENERGY TECHNOLOGY Co.,Ltd. Patentee before: DONGGUAN TAFEL NEW ENERGY TECHNOLOGY Co.,Ltd. Patentee before: SHENZHEN TAFEL NEW ENERGY TECHNOLOGY Co.,Ltd. |