CN107271609A - A kind of method for predicting ternary lithium titanate battery life cycle - Google Patents
A kind of method for predicting ternary lithium titanate battery life cycle Download PDFInfo
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- CN107271609A CN107271609A CN201710454898.3A CN201710454898A CN107271609A CN 107271609 A CN107271609 A CN 107271609A CN 201710454898 A CN201710454898 A CN 201710454898A CN 107271609 A CN107271609 A CN 107271609A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/3644—Constructional arrangements
- G01R31/3648—Constructional arrangements comprising digital calculation means, e.g. for performing an algorithm
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/392—Determining battery ageing or deterioration, e.g. state of health
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- G—PHYSICS
- G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
- G16Z—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS, NOT OTHERWISE PROVIDED FOR
- G16Z99/00—Subject matter not provided for in other main groups of this subclass
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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
- H01M10/4285—Testing apparatus
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to the method for predicting ternary lithium titanate battery life cycle.This method first to carry out predetermined number of times circulation after certain model specification ternary lithium titanate battery, carry out electrical property detection；Then disassemble, obtain the one or more in positive electrode, negative material, barrier film and electrolyte, and materialogy detection and/or analytical chemistry detection are carried out, set up the standard database on corresponding relation between ternary lithium titanate battery electrical performance indexes, materialogy parameter and/or analytical chemistry parameter and cycle-index；Take ternary lithium titanate battery to be measured equally to be disassembled and coherent detection again, compare, the remaining cycle-index of preestimating battery.The means such as comprehensive electrochemical properties test of the present invention, the materialogy detection of battery component and analytical chemistry detection, a set of relatively accurate evaluation ternary lithium titanate battery performance degradation degree and the method for predicting remaining life are proposed, more accurate foundation is provided for the echelon utilization of ternary lithium titanate battery.
Description
Technical field
The invention belongs to field of lithium, more particularly it relates to which a kind of be used to predict ternary-lithium titanate battery life
The method in life cycle.
Background technology
New energy power vehicle is developed rapidly in the case where the strategy of State-level is promoted, the waste and old electrokinetic cell produced therewith
Will since after 2018 rapid growth.In order to extend the course continuation mileage of new-energy automobile, the energy force density to electrokinetic cell will
Seek more and more higher, proportion of the ternary lithium battery in electrokinetic cell also more and more higher.And lithium titanate anode has excellent forthright again
Energy and cycle life performance, so ternary-lithium titanate battery is the trend of Future New Energy Source power vehicle development.
During due to electrokinetic cell hydraulic performance decline to 80%, new-energy automobile power battery Rejection standard is just reached, if directly
Connect and carry out these batteries to disassemble processing, it will cause the significant wastage of resource.Therefore, country is vigorously advocated to waste and old power electric
Pond realizes that echelon is utilized, and improves battery Life cycle use value.Waste and old power battery pack is unpacked, module is surveyed
Examination screening is assembled again, and echelon uses the fields such as the powered base station and street lamp, low-speed vehicle of energy storage or correlation.
But seldom the waste and old electrokinetic cell of recovery is utilized for echelon in the industry at present.On the one hand, because electrokinetic cell is advised
The quasi- disunity of case marker, state difference when scrapping is increased, and recycling difficulty is big.On the other hand, due to can not Accurate Prediction
The remaining life cycle of waste and old electrokinetic cell, the safety responsibility and after-sales service ownership after the utilization of battery echelon is not clear, is also resistance
The major reason for hindering the extensive echelon of electrokinetic cell to utilize.Therefore, realize that the echelon of electrokinetic cell is utilized, it is dynamic in the urgent need to carrying out
Power battery life cycle Predicting Technique, and accurate judgement can be made to remaining battery use value.
The Forecasting Methodology of current cycle life of lithium ion battery mainly has two classes：The first kind is the direct prediction based on experience
Method, using the Heuristics in battery use, the rough Statistics of battery life are provided according to some statistical laws, main to include following
Ring periodicity method, ampere-hour method and weighting ampere-hour method and event-oriented aging cumulative method.Equations of The Second Kind is indirect pre- based on performance
Survey method, including two processes：One is degenerate state identification, i.e., running state information, historical information and shape according to known to battery
The performance state of state monitoring information estimation battery is degenerated；Two be performance prediction, is become using certain algorithm estimated performance state evolution
Gesture.Above-mentioned two classes method, belongs to nondestructive evaluation method, the surplus value of prediction battery that can only be roughly, it is impossible to full
Sufficient echelon utilizes the demand accurately predicted waste and old electrokinetic cell residual life.
Due to the excellent performance of ternary-lithium titanate battery, even if after retired from new-energy automobile, still with higher
Use value, but lack a kind of remaining life cycle of ternary-metatitanic acid ternary-lithium titanate battery to scrapping at present and accurately predict
Method, the attenuation degree of the evaluation battery performance of all-dimensional multi-angle, so as to be waste and old ternary-metatitanic acid ternary-lithium titanate battery
Echelon utilizes and provides foundation.
The content of the invention
It is comprehensive the invention provides a kind of ternary-lithium titanate battery life cycle Forecasting Methodology in order to overcome drawbacks described above
The means such as the electric performance test of battery, the materialogy detection of battery component and analytical chemistry detection, are detected to old and useless battery
Analysis, and reference standards database, judge battery life, prediction of this method to battery life is relatively more accurate.
To achieve the above object, technical scheme is as follows：One kind is used to predict ternary-lithium titanate battery Life Cycle
The method of phase, comprises the following steps：
（1）To ternary-lithium titanate battery of certain model specification, after the circulation of predetermined number of times is carried out, electrical property detection is carried out；
The corresponding relation database that unit for electrical property parameters changes with cycle-index can be set up by the step；
（2）To step（1）The battery of middle process electrical property detection, is disassembled, obtain the positive electrode of battery, negative material,
One or more in barrier film and electrolyte；
（3）To step（2）One or more progress materials in positive electrode, negative material, barrier film and the electrolyte of middle acquisition
Learn detection and/or analytical chemistry detection；
（4）Set up corresponding relation on ternary-between lithium titanate battery electrical performance indexes and cycle-index standard database,
The standard database of corresponding relation between materialogy parameter and/or analytical chemistry parameter and cycle-index；
（5）Ternary-lithium titanate battery to be measured of the model specification is taken, electrical property detection is carried out, is then disassembled, three are obtained
One or more in positive electrode, negative material, barrier film and the electrolyte of member-lithium titanate battery；
（6）To step（5）One or more progress materials in positive electrode, negative material, barrier film and the electrolyte of middle acquisition
Learn and/or analytical chemistry detection, obtain materialogy index and/or analytical chemistry index parameter；
（7）By step（6）The materialogy index and/or analytical chemistry index parameter and step of middle acquisition（4）The standard of middle foundation
Database is compared, and judges the cycle-index that ternary-lithium titanate battery has been used, estimates remaining cycle-index.
Wherein, the positive electrode of the ternary-lithium titanate battery include nickel cobalt manganese material, one kind in nickel cobalt aluminum or
Two kinds；The negative material of the ternary-lithium titanate battery is mainly made up of lithium titanate（Metatitanic acid lithium content is negative material total amount
More than 50%）, or be made up of completely lithium titanate.
In the present invention, one cycle refers both to once complete charge and discharge cycles.Selection needs certain model specification reclaimed
Ternary-lithium titanate battery, after specified cycle-index, carry out electrical property detection.And electrical property is set up with circulation time
Number corresponding relation database.The battery of certain model specification refers to the battery of specific model to be recycled.Step（1）, step（2）
In, in order to obtain electric property and materialogy, the chemical property of the battery after different cycle-indexes, same batch can be selected
And multiple batteries under same model specification are detected and disassembled.Further, selection is with a batch of new battery.
Further, the nickel cobalt manganese（NCM）The molecular formula of material is LiNixCoyMn（1-x-y）O2, the nickel cobalt aluminium
（NCA）The molecular formula of material is LiNixCoyAl1-x-yO2Material, wherein 0<x<1,0<y<1.
Further, the nickel cobalt manganese（NCM）In material, nickel：Cobalt：The common mol ratio of manganese is 5:2:3、1:1:1、4:2:
4、6:2:2、8:1:One or more in 1, but be not limited to.
Further, nickel cobalt aluminium（NCA）In positive electrode, nickel：Cobalt：The common mol ratio of aluminium is 7:2:1 、8:1:1、8:
1.5:One or more in 0.5, but be not limited to.
Preferably, step（1）The cyclic process that middle ternary-lithium titanate battery carries out predetermined number of times is entered under specified requirements
Capable.Described specified conditions refer to what is carried out under the environmental conditions such as specific temperature, pressure, radiation.
Further, step（1）And step（5）Middle electrical property Testing index includes the discharge capacity of battery, discharge platform
One or more in voltage, internal resistance, energy, cycle efficieny, voltage decline, capacity retention rate and other electrical property detections.
Further, step（3）And step（6）In, materialogy detection and/or analytical chemistry detection are included to battery just
One or more progress materialogies and/or analytical chemistry detection in pole material, negative material, barrier film, electrolyte, further
Ground, described materialogy and/or analytical chemistry detection include to one kind in positive electrode, negative material, barrier film, electrolyte or
A variety of detection and analysis for carrying out structure/chemical composition.Preferably, the materialogy detection and/or analytical chemistry detection are included just
One or more in pole Structure analysis, negative pole structure constituent analysis, membrane configuration analysis, the constituent analysis of electrolyte.
Heretofore described materialogy detection is included to all parts（Refer to positive electrode, negative material, barrier film）Structural parameters enter
Row detection characterize, the structural parameters include surface topography, thickness, volume, porosity, crystal structure, granularity, crystal parameter,
Orientation texture；The chemical analysis parameter includes chemical constituent species, compound state, constituent content, each valency element ratio etc.
Chemical detection is analyzed.And set up the corresponding relation that corresponding detection parameter changes with cycle-index.Described corresponding relation includes
Set up the homologous thread of the parameter and cycle-index.
Further, step（3）And step（6）In, materialogy detection is carried out to positive electrode and/or analytical chemistry is detected
Ratio, the unit area/volume of the material changed including lattice constant in unit area/volume to cell positive material
The ratio for the material that middle unit cell volume changes, crystal grain average grain diameter, the content under certain element compound state, element always contain
One or more progress sign detections in amount, electric conductivity, granularity；
Materialogy detection and/or analytical chemistry detection are carried out to negative material includes unit area/body to cell negative electrode material
The ratio for the material that unit cell volume changes in the ratio for the material that lattice constant changes, unit area/volume in product,
One or more progress sign detections in crystal grain average grain diameter, the content under certain element compound state, certain element total content；
It is to referring to the electrolytic salt content in electrolyte, positive pole that materialogy detection and/or analytical chemistry detection are carried out to electrolyte
One or more in the content of active material, the content of negative electrode active material are detected；
The detection of the materialogy of battery diaphragm and/or analytical chemistry detection are included the porosity to barrier film, one kind in quality or
It is a variety of to be detected.
Further, step（3）And step（6）In, materialogy detection is carried out to positive electrode and/or analytical chemistry is detected
Including being carried out to cell positive material：X-ray diffraction is detected（XRD is detected）, analyze in positive electrode crystal structure, unit plane
The material that unit cell volume changes in the ratio for the material that lattice constant changes, unit area/volume in product/volume
One or more in ratio, crystal grain average grain diameter or other specification are with the increased changing rule of cycle-index；And/or X-ray
XPS Analysis is detected（XPS is detected）, analyze each element compound state in positive electrode and advised with the increased change of cycle-index
Rule, further refers to that each element is in the ratio of different compound states with the increased changing rule of cycle-index, further, institute
The element stated includes the one or more in Ni, Co, Mn, Al；And/or Inductively coupled plasma optical emission spectrometer detection（ICP-
OES is detected）, analysis positive electrode in each element content with the increased changing rule of cycle-index, further, described element
Including the one or more in Ni, Co, Mn, Al；And/or, positive conductive performance measurement, analysis positive plate electric conductivity is with circulation
The increased changing rule of number of times；And/or, positive pole powder granulometry, analysis positive electrode particle diameter becomes with cycle-index is increased
Law.
Further, step（3）And step（6）In, materialogy detection is carried out to positive electrode and/or analytical chemistry is detected
Including particle size determination, analysis positive electrode particle diameter is with the increased changing rule of cycle-index.
Further, step（3）And step（6）In, materialogy and/or analytical chemistry detection to lithium titanate anode include
GND is carried out：XRD detects that in analysis lithium titanate anode material crystal structure, lattice constant is sent out in unit area/volume
In the ratio of the material for changing, unit area/volume the average grain of the ratio for the material that unit cell volume changes, crystal grain or its
His parameter is with the increased changing rule of cycle-index；ICP-OES detects that each element content is with following in analysis lithium titanate anode material
The increased changing rule of ring number of times, further, described element include Ti, Li.
Further, step（3）And step（6）In, materialogy and/or analytical chemistry detection to barrier film are included to battery
Barrier film：Using fluid-discharge therapy, but it is not limited to, carries out porosity measurement, analysis barrier film porosity is advised with the increased change of cycle-index
Rule.
Further, step（3）And step（6）In, materialogy and/or analytical chemistry detection to electrolyte are included to electricity
Liquid is solved to carry out：HPLC-MS（LC-MS-MS）Electrolytic salt content is with circulation time in detection, analysis electrolyte
The increased changing rule of number, further, described electrolytic salt include LiPF6；ICP-OES detects that element contains in electrolyte
Dissolving positive pole, negative electrode active material content are with the increased changing rule of cycle-index in amount change, analysis electrolyte, further
Ground, described positive active material includes one or both of nickel cobalt manganese anode material, nickel cobalt aluminium positive electrode；Described is negative
Pole active material is metatitanic acid reason negative material.
To step（2）Positive electrode, negative material, barrier film and the electrolyte of middle acquisition carry out materialogy detection and analysisization
Detection is learned, materialogy index and analytical chemistry index parameter is obtained；To step（5）Ternary-lithium titanate battery to be measured of middle acquisition
Positive electrode, negative material, barrier film and electrolyte carry out materialogy and analytical chemistry detection, obtain ternary-lithium titanate to be measured
The materialogy index and analytical chemistry index parameter of battery.
Preferably, step（5）In take before ternary-lithium titanate battery to be measured the step of also including preliminary classification, that is, take some
Ternary-lithium titanate battery to be measured, carries out electrical property detection, is tentatively classified according to electrical property testing result.
Further, the preliminary classification refers to reject larger with electrical property deviation in a batch of ternary-lithium titanate
Ternary-lithium titanate battery, materialogy and analytical chemistry sampling Detection scope are not entered, is considered as no value battery.It is described inclined
Difference calculating benchmark can be as needed, by reclaim personnel determine, or using the average level of all batteries of same batch as
Calculating benchmark.Further, the larger ternary-lithium titanate battery of described deviation refers to that certain one or more of electric property is relative
In the battery of the average level of other batteries low 5%, preferably refer to low 10% battery, preferably refer to low 20% battery, enter
One step is preferably the battery of finger low 50%.Further, described electrical property include discharge capacity, it is discharge platform voltage, interior
Resistance, energy, cycle efficieny, voltage decline and capacity retention rate and other electrical properties.
Further, the larger ternary-lithium titanate battery of the deviation refers to that electric property is flat relative to other batteries
The battery of equal level low 5%, preferably refer to low 10% battery, preferably refer to low 20% battery, it is further preferred that refer to
Low 50% battery.
Further, by above-mentioned test, the electrical property of ternary-lithium titanate battery of certain model specification can be set up
Parameter and cycle-index, or unit for electrical property parameters and the corresponding relation of life-span/life cycle；Meanwhile, also set up model rule
Chemical composition/the structural parameters and cycle-index of ternary-lithium titanate battery of lattice, or material/structure parameter and life-span/life
The corresponding relation in cycle.Inventor has found after further investigation, the hydraulic performance decline of a certain part of ternary-lithium titanate battery
When, in the case that the performance of miscellaneous part is intact, performance/service life of battery also can be with the performance of the part
Drop and drastically decline, substantially reduce the service life of battery, during subsequent use, its life-span is primarily limited to the portion
Part.Thus, further, to improve system reliability, technical staff is according to life-span-electric property/knot of battery in database
Structure/chemical composition corresponding relation, and the result of the electricity, materialogy, chemical detection according to used batteries, it are substituted into respectively correspondence
In relation, according to corresponding corresponding relation, remaining service life is estimated, and choose most short remaining life（Or, most
Small cycles left number of times）As predicting the outcome.
Further, in the step（4）In, according to step（3）Middle different detection method, by each test parameter,
The standard comparison database changed with cycle-index is set up, finally by electrical performance indexes and materialogy and analytical chemistry index parameter
Collect, synthesis sets up standard comparison database.
In the optimal technical scheme that the present invention is provided, in the step（7）In, according to step（6）Detection and analysis result,
Compare step（4）The standard comparison database set up, judges the cycle-index that waste and old ternary-lithium titanate battery has been used,
Estimate remaining cycle-index.
Preferably, step（7）In, by electric property, materialogy and/or the analytical chemistry of ternary-lithium titanate battery to be measured
Testing result respectively with step（4）In standard database be compared, according to corresponding relation, estimate remaining cycle-index,
And the remaining cycle-index of minimum is chosen as predicting the outcome
Due to the particularity of ternary material self structure, determine that its cycle life is influenceed by following factor：First, cyclic process
The reconstruct of middle surface crystal structure.Second, second particle ruptures caused by anisotropic volumetric expansion in cyclic process.Therefore
For ternary-lithium titanate battery in the present invention, the analysis to positive pole material particle size is particularly important.
In addition, compared with carbon negative pole material, the potential of lithium titanate is high, and negative terminal surface is not likely to produce Li dendrite, is not easy to production
Raw SEI films, and lithium titanate material is that Volume Changes are minimum in zero strain material, battery charge and discharge process, is conducive to improving battery
Cycle performance.
Specific properties based on lithium titanate anode material, when the present invention is detected to negative material, because negative terminal surface
Hardly produce SEI films（Solid electrolyte interface film）, therefore negative terminal surface SEI films are to the life-span of ternary-lithium titanate battery
Influence is little.Meanwhile, because negative material is zero strain material, therefore without being detected to negative pole thickness.But need to titanium
The crystal structure of sour lithium material in itself is detected, analyzes the change of lithium titanate material structure in cyclic process.
Compared with prior art, the invention provides a kind of ternary-lithium titanate battery life cycle Forecasting Methodology, by right
In different model battery Life cycle, material structure composition transfer rule sets up the standard comparison on various size batteries
Database, can effectively disclose cell performance decay mechanism, while being waste and old ternary-lithium titanate battery remaining life（It is surplus
Remaining cycle-index）Relatively accurate basis for estimation is provided, is the production that waste and old ternary-metatitanic acid ternary-lithium titanate battery echelon is utilized
Product positioning provides evaluation method, overcomes and predicts battery using unit for electrical property parameters and the corresponding relation in cycle-index/life-span merely
The error that life-span brings.
Embodiment
Embodiment 1
A kind of ternary-lithium titanate battery life cycle Forecasting Methodology, methods described comprises the following steps：
（1）For the ternary-lithium titanate battery of certain model and specification, after designated cycle number of times, electrical property detection is carried out；
（2）To the battery detected by electrical property, disassembled, the positive electrode of acquisition battery, negative material, barrier film, electrolysis
Liquid；
（3）Materialogy and analytical chemistry detection are carried out to cell positive material, negative material, barrier film, electrolyte；
（4）The battery of the model specification is set up, is changed with cycle life, battery electrical property index, electrode material index parameter
Variation tendency standard database；
（5）By same specification waste and old ternary to be measured-metatitanic acid ternary-lithium titanate battery, electrical property detection is carried out, and tentatively divided
Level；
（6）To the old and useless battery after preliminary classification, sampling is disassembled, and obtains positive electrode, the negative pole material of old and useless battery
Material, barrier film, electrolyte；
（7）Materialogy and analytical chemistry detection are carried out to cell positive material, negative material, barrier film, electrolyte；
（8）The standard database set up is compared, the cycle-index that battery has been used is judged, estimates remaining cycle-index；
Wherein, the positive electrode of the ternary-lithium titanate battery is nickel cobalt manganese material；The negative pole of the ternary-lithium titanate battery
Material is made up of lithium titanate completely.
Wherein, the step（1）In, designated cycle number of times, according to the characteristic of ternary-lithium titanate battery, is chosen 200 times and followed
Central spacer sampling site, carries out electrical property detection to battery, including the discharge capacity of battery, discharge platform voltage, internal resistance, energy, follows
Ring efficiency, voltage decline and capacity retention rate.
Wherein, the step（2）In, battery is disassembled, in glove box, battery taken apart, by positive pole, negative pole and
Barrier film is peeled off, and respectively takes 10cm2Positive pole, negative pole and barrier film, using organic solvent such as propene carbonate（PC）, ethylene carbonate
（EC）, diethyl carbonate（DEC）, dimethyl carbonate（DMC）, methyl ethyl ester（EMC）Deng clear to positive pole and negative pole progress
Wash, each solvent load 5mL, clean three times altogether.By wash pools, test is remained standby.Meanwhile, by positive plate, negative plate and
Barrier film dries in glove box, is sealed up for safekeeping with hermetic bag, remains test standby.
Wherein, the step（3）In, materialogy and analytical chemistry detection are carried out to tertiary cathode to be included, by step（2）In
4 parts of ready tertiary cathode piece point.Take in wherein 1 part progress XRD detection, analysis tertiary cathode crystal structure, unit area
The ratio for the material that unit cell volume changes, crystal grain are put down in the ratio of the material that middle lattice constant changes, unit area
The parameters such as equal particle diameter are with the increased changing rule of cycle-index；Take in wherein 1 part progress XPS detection, analysis tertiary cathode material
The ratio of each compound state of each element is with the increased changing rule of cycle-index；Wherein 1 part is taken, 0.1 gram of tertiary cathode powder is scraped,
Dissolved using concentrated hydrochloric acid, be diluted to 20mL with deionized water, carry out Li in ICP-OES detections, analysis tertiary cathode material,
Ni, Co, Mn constituent content are with the increased changing rule of cycle-index；Wherein 1 part is taken, 0.1 gram of ternary lithium positive pole powder is scraped, adopts
With laser particle analyzer, positive electrode particle diameter is determined with the increased changing rule of cycle-index.
Wherein, the step（3）In, materialogy and analytical chemistry detection are carried out to lithium titanate anode to be included, by step 2
2 parts of ready lithium titanate anode piece point.Take in wherein 1 part progress XRD detection, analysis lithium titanate anode crystal structure, unit
The ratio for the material that unit cell volume changes, crystalline substance in the ratio for the material that lattice constant changes, unit area in area
The parameters such as grain average grain diameter are with the increased changing rule of cycle-index.Wherein 1 part is taken, 0.1 gram of lithium titanate anode powder is scraped, adopts
Dissolved with concentrated hydrochloric acid, concentrated nitric acid and oxidant, reducing agent, 20mL be diluted to deionized water, carry out ICP-OES detections,
Li constituent contents are with the increased changing rule of cycle-index in analysis lithium titanate anode material.
Wherein, the step（3）In, materialogy and analytical chemistry detection are carried out to barrier film to be included, by step（2）It is middle to prepare
Good barrier film.Take 5cm2, porosity measurement is carried out using fluid-discharge therapy, analysis barrier film porosity is advised with the increased change of cycle-index
Rule.
Wherein, the step（3）In, materialogy and analytical chemistry detection are carried out to electrolyte to be included, by step（2）It is middle to receive
2 parts of the cleaning fluid of collection point.Electrolytic salt content in wherein 1 part progress HPLC-MS detection, analysis electrolyte is taken to increase with cycle-index
Plus changing rule.Wherein 1 part is taken, oxidation processes are carried out using concentrated nitric acid, 20mL is diluted to deionized water, ICP- is carried out
OES detects that Li, Ni, Co, Mn constituent content change in electrolyte, and dissolving positive pole, negative electrode active material are with following in analysis electrolyte
The increased changing rule of ring number of times.
Wherein, the step（4）, according to step（1）And step（3）, obtain discharge capacity, the discharge platform electricity of battery
Pressure, internal resistance, energy, cycle efficieny, voltage decline and capacity retention rate, and ternary material positive pole, Carbon anode, barrier film, electrolysis
Liquid composition and structure set up basic database with the increased changing rule of cycle-index.
Wherein, the step（5）, electrical property detection, including electricity are carried out to waste and old ternary-lithium titanate battery of same specification
The discharge capacity in pond, discharge platform voltage, internal resistance, energy, cycle efficieny, voltage decline and capacity retention rate.Any parameter is inclined
From the battery of average value more than 10%, materialogy and analytical chemistry sampling Detection scope are not entered, is considered as no value battery.
Wherein, the step（6）, to step（5）It is middle by the battery that is tentatively classified, according to certain proportional sampling,
In glove box, battery is taken apart, positive pole, negative pole and barrier film are peeled off.According to step（2）Described in experimental method, tested
Sample preparation.
Wherein, the step（7）, according to step（3）Described in experimental method, to anode, negative pole, barrier film, electricity
Solve liquid and carry out materialogy and analytical chemistry detection.
Wherein, the step（8）, according to step（7）Test result, compare step（4）The standard database set up,
Judge the cycle-index that battery has been used, estimate remaining cycle-index, it is preferable that can be from minimum remaining circulation
Number of times is used as final result.
Embodiment 2
A kind of ternary-lithium titanate battery life cycle Forecasting Methodology, methods described comprises the following steps：
（1）For the ternary-lithium titanate battery of certain model and specification, after designated cycle number of times, electrical property detection is carried out；
（2）To the battery detected by electrical property, disassembled, the positive electrode of acquisition battery, negative material, barrier film, electrolysis
Liquid；
（3）Materialogy and analytical chemistry detection are carried out to cell positive material, negative material, barrier film, electrolyte；
（4）Different model and size battery cell are set up, is changed with cycle life, battery electrical property index, electrode material index parameter
Variation tendency standard database；
（5）By same specification waste and old ternary to be measured-metatitanic acid ternary-lithium titanate battery, electrical property detection is carried out, and tentatively divided
Level；
（6）To the old and useless battery after preliminary classification, sampling is disassembled, and obtains positive electrode, the negative pole material of old and useless battery
Material, barrier film, electrolyte；
（7）Materialogy and analytical chemistry detection are carried out to cell positive material, negative material, barrier film, electrolyte；
（8）The standard database set up is compared, the cycle-index that battery has been used is judged, estimates remaining cycle-index；
Wherein, the positive electrode of the ternary-lithium titanate battery is nickel cobalt aluminum；The negative pole of the ternary-lithium titanate battery
Material is made up of lithium titanate completely.
Wherein, the step（1）In, designated cycle number of times, according to the characteristic of ternary-lithium titanate battery, is chosen 300 times and followed
Central spacer sampling site, carries out electrical property detection to battery, including the discharge capacity of battery, discharge platform voltage, internal resistance, energy, follows
Ring efficiency, voltage decline and capacity retention rate.
Wherein, the step（2）In, battery is disassembled, in glove box, battery taken apart, by positive pole, negative pole and
Barrier film is peeled off, and respectively takes 10cm2Positive pole, negative pole and barrier film, using organic solvent such as propene carbonate（PC）, ethylene carbonate
（EC）, diethyl carbonate（DEC）, dimethyl carbonate（DMC）, methyl ethyl ester（EMC）Deng clear to positive pole and negative pole progress
Wash, each solvent load 5mL, clean three times altogether.By wash pools, test is remained standby.Meanwhile, by positive plate, negative plate and
Barrier film dries in glove box, is sealed up for safekeeping with hermetic bag, remains test standby.
Wherein, the step（3）In, materialogy and analytical chemistry detection are carried out to tertiary cathode to be included, by step（2）In
4 parts of ready tertiary cathode piece point.Take in wherein 1 part progress XRD detection, analysis tertiary cathode crystal structure, lattice constant,
The parameters such as unit cell volume, crystal grain average grain diameter are with the increased changing rule of cycle-index；Take wherein 1 part progress XPS detection, analysis
The ratio of each compound state of each element is with the increased changing rule of cycle-index in tertiary cathode material；Take wherein 1 part, scraping 0.1
Gram tertiary cathode powder, is dissolved using concentrated hydrochloric acid, and 20mL is diluted to deionized water, carries out ICP-OES detections, analysis three
Li, Ni, Co, Al constituent content are with the increased changing rule of cycle-index in first positive electrode；Wherein 1 part is taken, 0.1 gram three is scraped
First lithium positive pole powder, using laser particle analyzer, determines positive electrode particle diameter with the increased changing rule of cycle-index.
Wherein, the step（3）In, materialogy and analytical chemistry detection are carried out to lithium titanate anode to be included, by step 2
2 parts of ready lithium titanate anode piece point.Take in wherein 1 part progress XRD detection, analysis lithium titanate anode crystal structure, unit
The ratio for the material that unit cell volume changes, crystalline substance in the ratio for the material that lattice constant changes, unit area in area
The parameters such as grain average grain diameter are with the increased changing rule of cycle-index.Wherein 1 part is taken, 0.1 gram of lithium titanate anode powder is scraped, adopts
Dissolved with concentrated hydrochloric acid, concentrated nitric acid and oxidant, reducing agent, 20mL be diluted to deionized water, carry out ICP-OES detections,
Li constituent contents are with the increased changing rule of cycle-index in analysis lithium titanate anode material.
Wherein, the step（3）In, materialogy and analytical chemistry detection are carried out to barrier film to be included, by step（2）It is middle to prepare
Good barrier film.Take 5cm2, porosity measurement is carried out using fluid-discharge therapy, analysis barrier film porosity is advised with the increased change of cycle-index
Rule.
Wherein, the step（3）In, materialogy and analytical chemistry detection are carried out to electrolyte to be included, by step（2）It is middle to receive
2 parts of the cleaning fluid of collection point.Electrolytic salt content in wherein 1 part progress HPLC-MS detection, analysis electrolyte is taken to increase with cycle-index
Plus changing rule.Wherein 1 part is taken, oxidation processes are carried out using concentrated nitric acid, 20mL is diluted to deionized water, ICP- is carried out
OES detects that Li, Ni, Co, Al constituent content change in electrolyte, and dissolving positive pole, negative electrode active material are with following in analysis electrolyte
The increased changing rule of ring number of times.
Wherein, the step（4）, according to step（1）And step（3）, obtain discharge capacity, the discharge platform electricity of battery
Pressure, internal resistance, energy, cycle efficieny, voltage decline and capacity retention rate, and ternary material positive pole, Carbon anode, barrier film, electrolysis
Liquid composition and structure set up basic database with the increased changing rule of cycle-index.
Wherein, the step（5）, electrical property detection, including electricity are carried out to waste and old ternary-lithium titanate battery of same specification
The discharge capacity in pond, discharge platform voltage, internal resistance, energy, cycle efficieny, voltage decline and capacity retention rate.Any parameter is inclined
From the battery of average value more than 10%, materialogy and analytical chemistry sampling Detection scope are not entered, is considered as no value battery.
Wherein, the step（6）, to step（5）It is middle by the battery that is tentatively classified, according to certain proportional sampling,
In glove box, battery is taken apart, positive pole, negative pole and barrier film are peeled off.According to step（2）Described in experimental method, tested
Sample preparation.
Wherein, the step（7）, according to step（3）Described in experimental method, to anode, negative pole, barrier film, electricity
Solve liquid and carry out materialogy and analytical chemistry detection.
Wherein, the step（8）, according to step（7）Test result, compare step（4）The standard database set up,
Judge the cycle-index that battery has been used, estimate remaining cycle-index, it is preferable that can be from minimum remaining circulation
Number of times is used as final result.
Claims (9)
1. a kind of method for predicting ternary-lithium titanate battery life cycle, it is characterised in that comprise the following steps：
（1）To ternary-lithium titanate battery of certain model specification, after the circulation of predetermined number of times is carried out, electrical property detection is carried out；
（2）To step（1）The battery of middle process electrical property detection, is disassembled, obtain the positive electrode of battery, negative material,
One or more in barrier film and electrolyte；
（3）To step（2）One or more progress materials in positive electrode, negative material, barrier film and the electrolyte of middle acquisition
Learn detection and/or analytical chemistry detection；
（4）Set up the corresponding relation of the ternary-between lithium titanate battery electrical performance indexes and cycle-index on the model specification
Standard database, between materialogy parameter and/or analytical chemistry parameter and cycle-index corresponding relation standard database；
（5）Ternary-lithium titanate battery to be measured of the model specification is taken, electrical property detection is carried out, is then disassembled, three are obtained
One or more in positive electrode, negative material, barrier film and the electrolyte of member-lithium titanate battery；
（6）To step（5）One or more progress materials in positive electrode, negative material, barrier film and the electrolyte of middle acquisition
Learn and/or analytical chemistry detection, obtain materialogy index and/or analytical chemistry index parameter；
（7）By step（6）The materialogy index and/or analytical chemistry index parameter and step of middle acquisition（4）The standard of middle foundation
Database is compared, and judges the cycle-index that ternary-lithium titanate battery has been used, estimates remaining cycle-index；
Wherein, the positive electrode of the ternary-lithium titanate battery includes nickel cobalt manganese material, one kind in nickel cobalt aluminum or two
Kind；The negative material of the ternary-lithium titanate battery is mainly made up of lithium titanate, or is made up of completely lithium titanate.
2. the method for predicting ternary-lithium titanate battery life cycle according to claim 1, it is characterised in that
The molecular formula of the nickel cobalt manganese material is LiNixCoyMn（1-x-y）O2, the molecular formula of the nickel cobalt aluminum is LiNixCoyAl1-x- yO2, wherein 0<x<1,0<y<1.
3. the method for predicting ternary-lithium titanate battery life cycle according to claim 1, it is characterised in that
Step（1）And step（5）The discharge capacity of middle electrical property Testing index including battery, discharge platform voltage, internal resistance, energy, follow
One or more in ring efficiency, voltage decline, capacity retention rate.
4. the method according to claim 1 for predicting lithium battery life cycle, it is characterised in that the materialogy inspection
Surveying includes carrying out the structural parameters of all parts detection sign, and the structural parameters include surface topography, thickness, volume, matter
One or more in amount, porosity, crystal structure, granularity, crystal parameter, orientation texture；The analytical chemistry parameter includes
One or more in chemical constituent species, chemical constituent content, element compounds state, constituent content, each element valence state ratio.
5. the method for predicting ternary-lithium titanate battery life cycle according to claim 1, it is characterised in that
Step（3）And step（6）In, materialogy detection and/or analytical chemistry detection are carried out to positive electrode to be included to anode material
Unit cell volume becomes in the ratio for the material that lattice constant changes, unit area/volume in unit area/volume of material
In the ratio of the material of change, crystal grain average grain diameter, the content under certain element compound state, element total content, electric conductivity, granularity
One or more carry out sign detections；
Materialogy detection and/or analytical chemistry detection are carried out to negative material includes unit area/body to cell negative electrode material
The ratio for the material that unit cell volume changes in the ratio for the material that lattice constant changes, unit area/volume in product,
One or more progress sign detections in crystal grain average grain diameter, the content under certain element compound state, certain element total content；
It is to referring to the electrolytic salt content in electrolyte, positive pole that materialogy detection and/or analytical chemistry detection are carried out to electrolyte
One or more in the content of active material, the content of negative electrode active material are detected；
The detection of the materialogy of battery diaphragm and/or analytical chemistry detection are included the porosity to barrier film, one kind in quality or
It is a variety of to be detected.
6. the method for predicting ternary-lithium titanate battery life cycle according to claim 1, it is characterised in that
Step（3）And step（6）In, detected using XRD, it is brilliant in unit area/volume in analysis positive pole, negative material crystal structure
The ratio for the material that unit cell volume changes, crystal grain are put down in the ratio of the material that lattice constant changes, unit area/volume
One or more in equal particle diameter or other specification are with the increased changing rule of cycle-index；And/or using XPS detections, analysis
Each element compound state is with the increased changing rule of cycle-index in positive electrode, negative material, further including each element at
In different compound states ratio with the increased changing rule of cycle-index；And/or using ICP-OES detections, analysis positive pole, negative pole
Each element content is with the increased changing rule of cycle-index in material；And/or positive pole electric conductivity is measured, analyze positive pole
Piece electric conductivity is with the increased changing rule of cycle-index；And/or positive pole powder size is measured, analysis positive electrode grain
Footpath is with the increased changing rule of cycle-index；And/or using HPLC-MS detections, electrolytic salt content is with following in analysis electrolyte
The increased changing rule of ring number of times；And/or using ICP-OES detections, analyze constituent content in electrolyte and change, analyze electrolyte
Middle dissolving positive pole, negative electrode active material content are with the increased changing rule of cycle-index.
7. the method for predicting ternary-lithium titanate battery life cycle according to any one of claim 1-6, it is special
Levy and be, step（3）And step（6）In, materialogy detection and/or analytical chemistry detection are carried out to positive electrode includes powder grain
Degree is determined, and analysis positive electrode particle diameter is with the increased changing rule of cycle-index；
Materialogy and/or analytical chemistry detection to lithium titanate anode include, and lithium titanate anode material crystal is analyzed in XRD detections
In structure, unit cell volume is sent out in the ratio for the material that lattice constant changes, unit area/volume in unit area/volume
The average grain of the ratio of the material for changing, crystal grain or other specification are with the increased changing rule of cycle-index；ICP-OES detections,
Each element content is with the increased changing rule of cycle-index in analysis lithium titanate anode material.
8. the method for predicting ternary-lithium titanate battery life cycle according to any one of claim 1-6, it is special
Levy and be, to step（2）Positive electrode, negative material, barrier film and the electrolyte of middle acquisition carry out materialogy detection and analysisization
Detection is learned, materialogy index and analytical chemistry index parameter is obtained；To step（5）Ternary-lithium titanate battery to be measured of middle acquisition
Positive electrode, negative material, barrier film and electrolyte carry out materialogy and analytical chemistry detection, obtain ternary-lithium titanate to be measured
The materialogy index and analytical chemistry index parameter of battery.
9. the method for predicting ternary-lithium titanate battery life cycle according to any one of claim 1-6, it is special
Levy and be, step（7）In, by the electric property of ternary-lithium titanate battery to be measured, materialogy and/or analytical chemistry testing result
Respectively with step（4）In standard database be compared, according to corresponding relation, estimate remaining cycle-index, and choose most
Small remaining cycle-index is as predicting the outcome.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112534626A (en) * | 2018-08-06 | 2021-03-19 | 美蓓亚三美株式会社 | System and method for determining deterioration of secondary battery |
| CN113740404A (en) * | 2021-09-03 | 2021-12-03 | 厦门厦钨新能源材料股份有限公司 | Method for nondestructive evaluation of molar ratio of lithium to cobalt in lithium battery electrode |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104466230A (en) * | 2013-09-13 | 2015-03-25 | 浙江万向亿能动力电池有限公司 | Lithium titanate battery based on lithium-enriched manganese anode and charging method thereof |
| CN105005001A (en) * | 2015-06-26 | 2015-10-28 | 江苏北新能源科技有限公司 | Method for rapidly detecting remaining use times of battery |
-
2017
- 2017-06-16 CN CN201710454898.3A patent/CN107271609A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104466230A (en) * | 2013-09-13 | 2015-03-25 | 浙江万向亿能动力电池有限公司 | Lithium titanate battery based on lithium-enriched manganese anode and charging method thereof |
| CN105005001A (en) * | 2015-06-26 | 2015-10-28 | 江苏北新能源科技有限公司 | Method for rapidly detecting remaining use times of battery |
Non-Patent Citations (2)
| Title |
|---|
| 李翔等: "锂离子电池循环寿命影响因素分析", 《电源技术》 * |
| 闫春秋: "锂离子电池富镍三元材料振实密度与一次颗粒研究", 《中国优秀硕士学位论文全文数据库 工程科技II辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112534626A (en) * | 2018-08-06 | 2021-03-19 | 美蓓亚三美株式会社 | System and method for determining deterioration of secondary battery |
| CN112534626B (en) * | 2018-08-06 | 2024-03-22 | 美蓓亚三美株式会社 | Secondary battery degradation determination system and degradation determination method |
| CN113740404A (en) * | 2021-09-03 | 2021-12-03 | 厦门厦钨新能源材料股份有限公司 | Method for nondestructive evaluation of molar ratio of lithium to cobalt in lithium battery electrode |
| CN113740404B (en) * | 2021-09-03 | 2023-10-27 | 厦门厦钨新能源材料股份有限公司 | Method for nondestructively evaluating lithium cobalt molar ratio in lithium battery electrode |
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