CN117706386B - Calculation method and device for upper limit and lower limit of lithium intercalation coefficient of anode and cathode of lithium battery - Google Patents
Calculation method and device for upper limit and lower limit of lithium intercalation coefficient of anode and cathode of lithium battery Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 377
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 377
- 230000002687 intercalation Effects 0.000 title claims abstract description 319
- 238000009830 intercalation Methods 0.000 title claims abstract description 319
- 238000004364 calculation method Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims description 36
- 239000007773 negative electrode material Substances 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 230000006870 function Effects 0.000 claims description 13
- 238000009831 deintercalation Methods 0.000 claims description 4
- 238000004422 calculation algorithm Methods 0.000 claims description 3
- 238000005457 optimization Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 238000010586 diagram Methods 0.000 description 11
- 238000003780 insertion Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 230000037431 insertion Effects 0.000 description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- 238000004088 simulation Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 238000002939 conjugate gradient method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007637 random forest analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002922 simulated annealing Methods 0.000 description 1
- 238000002945 steepest descent method Methods 0.000 description 1
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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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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a calculation method of upper and lower limits of lithium intercalation coefficients of a positive electrode and a negative electrode of a lithium battery, which comprises the following steps: reading a plurality of battery curves input by a user; setting an upper limit initial interval and a lower limit initial interval of a positive-negative electrode lithium intercalation coefficient; forming a lithium intercalation coefficient group by arbitrarily taking values from each initial interval respectively; calculating the state of charge of the positive electrodeState of charge of negative electrode，For battery state of charge in a first full battery curveAnd calculating the positive open circuit voltage according to the positive charge state and the negative charge stateOpen circuit voltage of negative electrodeAnd battery open circuit voltageObtaining a second full cell curve; calculating the error between the second full-battery curve and the first full-battery curve, changing the values of different lithium intercalation coefficient groups in each initial interval, and searching the upper limit and the lower limit of the lithium intercalation coefficient of the positive electrode and the negative electrode of the lithium battery corresponding to the minimum error; the device, the electronic equipment and the storage medium are used for calculating the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of the lithium battery; the calculation method can shorten the time for obtaining the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of the lithium battery.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a method and a device for calculating upper and lower limits of lithium intercalation coefficients of positive and negative electrodes of a lithium battery.
Background
In the process of simulating and calculating the performance of the lithium battery, the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode are one of indispensable parameters. The lithium intercalation coefficient refers to the ratio of the concentration of lithium ions in an electrode material to the maximum lithium ion concentration that the material can achieve. This ratio is a dimensionless number, typically varying between 0 and 1, that describes the extent of intercalation and deintercalation of lithium ions into the electrode material during charge and discharge. It is commonly denoted as Li-insertion coefficient, also known as lithium reversible capacity (lithium reversible capacity) or lithium insertion/extraction capacity (lithium insertion/extraction capacity).
Because of the difficulty and complexity of the experiment, users often need to spend a great deal of time to obtain the upper limit and the lower limit of the lithium intercalation coefficient, the efficiency is low, the cost is high, and the simulation calculation and the research and the development of the lithium battery are not facilitated.
Disclosure of Invention
In order to overcome the defects in the prior art, the embodiment of the invention provides a method and a device for calculating the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of a lithium battery, electronic equipment and a storage medium.
In order to achieve the above purpose, the invention adopts the following technical scheme:
In a first aspect, a method for calculating an upper limit and a lower limit of a lithium intercalation coefficient of a positive electrode and a negative electrode of a lithium battery includes the following steps:
reading an anode half-battery curve, a cathode half-battery curve and a full-battery SOC-OCV curve which are input by a user, and taking the full-battery SOC-OCV curve as a first full-battery curve;
Setting an upper limit initial interval and a lower limit initial interval of a positive electrode lithium intercalation coefficient, wherein the upper limit initial interval, the lower limit initial interval, the upper limit initial interval and the lower limit initial interval of the positive electrode lithium intercalation coefficient, the negative electrode lithium intercalation coefficient are respectively set;
the values are arbitrarily taken from each initial interval to obtain the lower limit of the lithium intercalation coefficient of the positive electrode Positive electrode lithium intercalation coefficient upper limit/>Lower limit of lithium intercalation coefficient of negative electrode/>And the upper limit of the lithium intercalation coefficient of the negative electrode/>A lithium intercalation coefficient group formed;
Lower limit of lithium intercalation coefficient from positive electrode Positive electrode lithium intercalation coefficient upper limit/>And calculating a positive state of charge/>, of the battery state of charge, SOC, in the first full-battery curveLithium intercalation coefficient lower limit/>, from negative electrodeUpper limit of lithium intercalation coefficient of negative electrode/>And calculating a negative electrode state of charge (SOC) from the SOC in the first full-cell curveWherein, the positive electrode inserts lithium interval/>Negative electrode lithium intercalation intervalX is the battery state of charge SOC in the first full battery curve;
Calculating a corresponding positive open circuit voltage OCV pos according to the positive charge state SOC pos and the positive half-cell curve; calculating a corresponding anode open circuit voltage OCV neg according to the anode charge state SOC neg and the anode half-cell curve, and calculating a battery open circuit voltage ocv=ocv pos-OCVneg to obtain a second full-cell curve corresponding to the lithium intercalation coefficient group;
Calculating the error between the second full battery curve and the first full battery curve, changing the value in each initial interval to obtain different lithium intercalation coefficient groups, and searching the optimal lithium intercalation coefficient group corresponding to the minimum error, wherein the optimal lithium intercalation coefficient group is the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of the lithium battery.
When the positive state of charge SOC pos and the negative state of charge SOC neg are calculated, the battery state of charge SOC may be taken at any interval in the first full-battery curve, for example, x= {0,0.01,0.02.. 0.98,0.99,1}, the positive state of charge SOC pos and the negative state of charge SOC neg corresponding to different battery states of charge SOCs are calculated, and further, the battery open circuit voltage OCV corresponding to different battery states of charge SOCs is calculated, and the second full-battery curve corresponding to the lithium intercalation coefficient group is obtained.
Calculating a corresponding positive open circuit voltage OCV pos according to the positive charge state SOC pos and the positive half-cell curve; the corresponding negative open circuit voltage OCV neg is calculated from the negative state of charge SOC neg and the negative half-cell curve, and the cell open circuit voltage ocv=ocv pos-OCVneg is calculated. The calculation methods used therein include, but are not limited to, linear interpolation, spline interpolation, polynomial fitting, piecewise polynomial fitting, and the like.
Calculating the error between the second full cell curve and the first full cell curve may be by calculating the distance between the first full cell curve and the second full cell curve.
Preferably, when the user sets the actual gram capacity of the positive electrode active material, the theoretical gram capacity of the positive electrode active material, the actual gram capacity of the negative electrode active material and the theoretical gram capacity of the negative electrode active material, the setting of the initial interval of the upper and lower limits of the positive and negative electrode lithium intercalation coefficient includes:
Calculating the lithium intercalation interval of the positive electrode Calculating a negative electrode lithium intercalation intervalWherein the NP ratio is the ratio of the capacity of the negative electrode and the capacity of the positive electrode of the battery;
Setting the initial interval of the lithium intercalation coefficient lower limit of the positive electrode Positive electrode lithium intercalation coefficient upper limit initial zone/>Initial interval of negative electrode lithium intercalation coefficient lower limitInitial interval of upper limit of lithium intercalation coefficient of negative electrode/>And 0.5 is a set negative electrode degree of freedom, and the negative electrode degree of freedom can be arbitrarily valued under the condition that the upper limit of the negative electrode lithium intercalation coefficient is larger than the lower limit of the negative electrode lithium intercalation coefficient.
The above calculation is applicable to the actual gram capacity of the half-cell provided by the user. When the user provides the actual gram capacity of the full battery, the calculation of the negative electrode lithium intercalation interval does not need to divide the NP ratio. The NP ratio is a cell design parameter and is directly provided by a user. Since there is an error in determining the negative electrode lithium intercalation coefficient interval of the full cell from the actual gram capacity of the negative electrode half cell, the degree of freedom of the negative electrode is set when the negative electrode lithium intercalation coefficient interval is set.
Further preferably, after the positive electrode lithium insertion section Δχ pos and the negative electrode lithium insertion section Δχ neg are obtained, before setting the positive electrode and negative electrode lithium insertion coefficient upper and lower limit initial sections, the method further comprises:
Verifying data interval of positive half-cell curve input by user Whether or not to meet/>Data interval/>, of negative half-cell curve input by userWhether or not to meet/>
If yes, continuing to set an initial interval of the upper limit and the lower limit of the lithium intercalation coefficient;
and if the data do not meet the data, supplementing the positive half-cell curve and the negative half-cell curve.
Further preferably, when the user gives the positive electrode active material actual gram capacity, the positive electrode active material component, the negative electrode active material actual gram capacity, and the negative electrode active material component, the setting of the positive and negative electrode lithium intercalation coefficient upper and lower limit initial intervals includes:
Calculation of
Wherein M pos is the molar mass of the positive electrode active material, M neg is the molar mass of the negative electrode active material, the unit is g/mol, F is Faraday constant, n is the number of electrons participating in the lithium deintercalation reaction, and C is the unit coulomb of the charge quantity;
Calculating the lithium intercalation interval of the positive electrode Negative electrode lithium intercalation interval
Setting the initial interval of the lithium intercalation coefficient lower limit of the positive electrodePositive electrode lithium intercalation coefficient upper limit initial zone/>Initial interval of negative electrode lithium intercalation coefficient lower limitInitial interval of upper limit of lithium intercalation coefficient of negative electrode/>
In general, the setting the initial interval of the upper and lower limits of the positive and negative lithium intercalation coefficients includes:
Setting the initial interval of the lithium intercalation coefficient lower limit of the positive electrode Initial interval of positive electrode lithium intercalation coefficient upper limitInitial interval of negative electrode lithium intercalation coefficient lower limit/>Initial interval of upper limit of lithium intercalation coefficient of negative electrode
Preferably, calculating the error between the second full cell curve and the first full cell curve includes:
A LOSS function is constructed and the function, Wherein, OCV i 1 is the first open-circuit voltage in the first full-cell curve, OCV i 2 is the second open-circuit voltage in the second full-cell curve, n is the data logarithm selected for calculating the error, i is the number of n pairs of data.
Preferably, the values are changed in each initial interval to obtain different lithium intercalation coefficient groups, and the optimal lithium intercalation coefficient group corresponding to the minimum error is searched. The parameter optimization algorithm comprises, but is not limited to, a steepest descent method, a Newton method, a quasi-Newton method, a conjugate gradient method, sequential quadratic programming, simulated annealing, a genetic algorithm, random forest, bayesian optimization, random search and the like. The traversal includes, but is not limited to, uniform step traversal, random step traversal, adaptive step traversal, and the like. The values can be respectively taken in the positive electrode lithium intercalation coefficient lower limit initial section, the positive electrode lithium intercalation coefficient upper limit initial section, the negative electrode lithium intercalation coefficient lower limit initial section and the negative electrode lithium intercalation coefficient upper limit initial section. The value can also be taken in the initial interval of the lower limit of the lithium intercalation coefficient of the positive electrode or the initial interval of the upper limit of the lithium intercalation coefficient of the positive electrode, and the lithium intercalation interval is passedAnd calculating the value of the upper limit of the corresponding positive electrode lithium intercalation coefficient or the value of the lower limit of the positive electrode lithium intercalation coefficient. The values of the upper limit of the negative electrode lithium intercalation coefficient or the lower limit of the negative electrode lithium intercalation coefficient can be the same as the above.
A second aspect of the present invention is an apparatus for calculating an upper limit and a lower limit of a lithium intercalation coefficient of an anode and a cathode of a lithium battery, comprising:
The data acquisition unit is used for reading the positive half-battery curve, the negative half-battery curve and the full-battery SOC-OCV curve input by a user, and taking the full-battery SOC-OCV curve as a first full-battery curve;
The initial section determining unit is used for setting an upper limit initial section and a lower limit initial section of the positive and negative electrode lithium intercalation coefficient, and comprises setting an upper limit initial section, a lower limit initial section, an upper limit initial section and a lower limit initial section of the positive and negative electrode lithium intercalation coefficient respectively;
a lithium intercalation coefficient group selecting unit for arbitrarily selecting values from each initial interval to obtain the lower limit of the lithium intercalation coefficient of the positive electrode Positive electrode lithium intercalation coefficient upper limit/>Lower limit of lithium intercalation coefficient of negative electrode/>And the upper limit of the lithium intercalation coefficient of the negative electrode/>A lithium intercalation coefficient group formed;
A data calculation unit for calculating the state of charge of the positive electrode Negative state of chargeWherein, the positive electrode inserts lithium interval/>Negative electrode lithium intercalation intervalX is the battery state of charge SOC in the first full battery curve; calculating a corresponding positive open circuit voltage OCV pos according to the positive charge state SOC pos and the positive half-cell curve, calculating a corresponding negative open circuit voltage OCV neg according to the negative charge state SOC neg and the negative half-cell curve, and calculating a battery open circuit voltage OCV=OCV pos-OCVneg to obtain a second full-cell curve corresponding to the lithium intercalation coefficient group;
And the error comparison unit is used for calculating the error between the second full battery curve and the first full battery curve, changing the value in each initial interval to obtain different lithium intercalation coefficient groups, and searching the optimal lithium intercalation coefficient group corresponding to the minimum error, wherein the optimal lithium intercalation coefficient group is the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of the lithium battery.
The electronic equipment comprises a memory and a processor, wherein at least one program instruction is stored in the memory, and the processor is used for realizing the calculation method of the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of the lithium battery by loading and executing the at least one program instruction.
A computer storage medium, in which at least one program instruction is stored, where the at least one program instruction is loaded and executed by a processor to implement the method for calculating the upper limit and the lower limit of the positive and negative lithium intercalation coefficient of the lithium battery.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
The upper limit and the lower limit of the lithium battery anode-cathode lithium intercalation coefficient can be obtained through calculation by utilizing information provided by a user, so that the process of obtaining the upper limit and the lower limit of the lithium battery anode-cathode lithium intercalation coefficient through experiments is avoided, the research and development cost is reduced, the simulation calculation efficiency is improved, and the research and development process of the battery is accelerated.
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of preferred embodiments, as illustrated in the accompanying drawings.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a calculation method in an embodiment of the invention;
FIG. 2 is a schematic diagram of a positive half-cell in accordance with one embodiment of the present invention;
FIG. 3 is a schematic diagram of a negative half-cell in accordance with an embodiment of the present invention;
FIG. 4 is a schematic diagram of a full battery SOC-OCV curve in accordance with an embodiment of the present invention;
FIG. 5 is a graph showing the comparison of the second full cell curve and the first full cell curve in the first embodiment of the present invention;
FIG. 6 is a schematic diagram of a positive half-cell in accordance with a second embodiment of the present invention;
FIG. 7 is a schematic diagram of a negative half-cell in accordance with a second embodiment of the present invention;
FIG. 8 is a diagram illustrating a full battery SOC-OCV curve in accordance with a second embodiment of the present invention;
FIG. 9 is a graph showing the comparison of the second full cell curve and the first full cell curve in the second embodiment of the present invention;
FIG. 10 is a schematic view of a positive half-cell in accordance with a third embodiment of the present invention;
FIG. 11 is a schematic view of a negative half-cell in accordance with a third embodiment of the present invention;
FIG. 12 is a schematic diagram of a full battery SOC-OCV curve in accordance with an embodiment of the present invention;
Fig. 13 is a diagram showing the comparison of the second full cell curve and the first full cell curve in the third embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one: ternary lithium batteries were selected for this example. As shown in fig. 2, is a positive half-cell curve entered by the user. As shown in fig. 3, is a negative half-cell curve for user input. As shown in fig. 4, is a full battery SOC-OCV curve entered by the user. The actual gram capacity of the positive electrode active material of the lithium battery is 183.48mAh/g, the theoretical gram capacity of the positive electrode active material is 278mAh/g, the actual gram capacity of the negative electrode active material is 365mAh/g, the theoretical gram capacity of the negative electrode active material is 372mAh/g, and the NP ratio=1.138.
Referring to fig. 1, the method for calculating the upper and lower limits of the lithium intercalation coefficient of the positive and negative electrodes of the ternary lithium battery comprises the following steps:
step 101: reading user input data;
The method comprises the following steps: and reading the positive half-battery curve, the negative half-battery curve and the full-battery SOC-OCV curve input by a user, and taking the full-battery SOC-OCV curve as a first full-battery curve. Obtaining the minimum value of the positive electrode lithium intercalation coefficient in the positive electrode half-cell curve Maximum value/>, of positive electrode lithium intercalation coefficient in positive electrode half-cell curveMinimum value of negative electrode lithium intercalation coefficient in negative electrode half-cell curve/>Maximum value/>, of negative electrode lithium intercalation coefficient in negative electrode half-cell curveObtaining data interval/>, of positive half-cell curveObtaining data interval/>, of negative half-cell curve
Step 102: setting an upper limit initial interval and a lower limit initial interval of a positive-negative electrode lithium intercalation coefficient;
The method comprises the following steps: calculating the lithium intercalation interval of the positive electrode Calculating the lithium intercalation interval/>, of the negative electrode
Verifying data interval of positive half-cell curve input by userWhether or not to meet/>Data interval/>, of negative half-cell curve input by userWhether or not to meet/>
Setting the initial interval of the lithium intercalation coefficient lower limit of the positive electrodePositive electrode lithium intercalation coefficient upper limit initial zone/>Initial interval of negative electrode lithium intercalation coefficient lower limitInitial interval of upper limit of lithium intercalation coefficient of negative electrode/>0.5 Is the set negative electrode degree of freedom.
Step 103: selecting a lithium intercalation coefficient group;
the method comprises the following steps: initial interval of lower limit of lithium intercalation coefficient from positive electrode Selecting any value as the lower limit/>, of the lithium intercalation coefficient of the positive electrodeInitial interval of upper limit of lithium intercalation coefficient from positive electrodeSelecting any value as the upper limit/>, of the positive electrode lithium intercalation coefficientInitial interval/>, from lower limit of lithium intercalation coefficient of negative electrodeSelecting any value as the lower limit/>, of the negative electrode lithium intercalation coefficientInitial interval/>, from upper limit of lithium intercalation coefficient of negative electrodeSelecting any value as the upper limit/>, of the lithium intercalation coefficient of the cathodeFrom the lower limit of the lithium intercalation coefficient of the positive electrode/>Positive electrode lithium intercalation coefficient upper limit/>Lower limit of lithium intercalation coefficient of negative electrode/>And the upper limit of the lithium intercalation coefficient of the negative electrode/>And forming a lithium intercalation coefficient group.
Step 104: calculating a second full cell curve;
The method comprises the following steps: lower limit of lithium intercalation coefficient from positive electrode Positive electrode lithium intercalation coefficient upper limit/>And calculating a positive state of charge/>, of the battery state of charge, SOC, in the first full-battery curveLithium intercalation coefficient lower limit/>, from negative electrodeUpper limit of lithium intercalation coefficient of negative electrode/>And calculating a negative state of charge/>, of the battery state of charge, SOC, in the first full-battery curveWhere X is the battery state of charge SOC in the first full battery curve. And calculating the positive electrode charge state SOC pos and the negative electrode charge state SOC neg corresponding to the different battery charge states SOC by taking the battery charge state SOC at any interval in the first full battery curve.
And calculating the corresponding positive electrode open circuit voltage OCV pos according to the positive electrode charge state SOC pos and the positive electrode half-cell curve. The corresponding negative open circuit voltage OCV neg is calculated from the negative state of charge SOC neg and the negative half-cell curve, and the cell open circuit voltage ocv=ocv pos-OCVneg is calculated. And obtaining a second full-battery curve corresponding to the lithium intercalation coefficient group by using the battery charge state SOC and the battery open circuit voltage OCV which are corresponding to the plurality of groups.
Step 105: calculating an error to obtain an optimal lithium intercalation coefficient;
the method comprises the following steps: a LOSS function is constructed and the function, Wherein OCV i 1 is the first open circuit voltage in the first full-cell curve, OCV i 2 is the second open circuit voltage in the second full-cell curve (i.e., the open circuit voltage of the battery calculated in step 104), n is the logarithm of the data selected for calculating the error, and i is the number of n pairs of data.
The error value at the set of lithium intercalation coefficients is determined from the LOSS function. And repeating the steps 103-105, and obtaining corresponding second full battery curves and corresponding error values when different lithium intercalation coefficient groups are obtained. Taking a group of lithium intercalation coefficients with the minimum error value as an optimal lithium intercalation coefficient group, wherein the lower limit of the positive electrode lithium intercalation coefficient in the optimal lithium intercalation coefficient groupPositive electrode lithium intercalation coefficient upper limit/>Lower limit of lithium intercalation coefficient of negative electrode/>And the upper limit of the lithium intercalation coefficient of the negative electrode/>The upper limit and the lower limit of the lithium intercalation coefficient of the positive electrode and the negative electrode of the lithium battery are obtained.
When the loss=0.005 is calculated, the optimal lithium intercalation coefficient group is obtained, and the loss=0.005 indicates that the deviation between the calculated second full-cell curve and the actual first full-cell curve is small. The lower limit of the lithium intercalation coefficient of the positive electrode in the optimal lithium intercalation coefficient groupPositive electrode lithium intercalation coefficient upper limit/>Lower limit of lithium intercalation coefficient of negative electrode/>Upper limit of lithium intercalation coefficient of negative electrode/>
The lower limit of the lithium intercalation coefficient of the positive electrode of the lithium battery obtained through experimentsUpper limit of lithium intercalation coefficient of positive electrodeLower limit of lithium intercalation coefficient of negative electrode/>Upper limit of lithium intercalation coefficient of negative electrode/>Fig. 5 is a schematic diagram showing the comparison of the second full cell curve and the first full cell curve at the optimal lithium intercalation coefficient set. It can also be obtained from the graph that the calculated second full cell curve substantially coincides with the true first full cell curve, and the deviation between the two is small and substantially negligible. Therefore, the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of the lithium battery, which are determined by the calculation method of the application, can be used for the performance simulation calculation of the lithium battery.
Embodiment two: as shown in fig. 6 to 9, in this example, a lithium iron phosphate battery was used, the positive electrode active material was lithium iron phosphate, and the negative electrode active material was graphite. The actual gram capacity of the positive electrode active material input into the full cell is 142mAh/g, and the actual gram capacity of the negative electrode active material input into the full cell is 340mAh/g. As shown in fig. 6, is a positive half-cell curve entered by the user. As shown in fig. 7, is a negative half-cell curve entered by the user. As shown in fig. 8, is a full battery SOC-OCV curve entered by the user.
The calculation method of the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of the lithium iron phosphate battery comprises the following steps:
step 201: reading user input data;
The method comprises the following steps: and reading the positive half-battery curve, the negative half-battery curve and the full-battery SOC-OCV curve input by a user, and taking the full-battery SOC-OCV curve as a first full-battery curve.
Step 202: setting an upper limit initial interval and a lower limit initial interval of a positive-negative electrode lithium intercalation coefficient;
The method comprises the following steps: setting minimum value of positive electrode lithium intercalation coefficient Minimum value of lithium intercalation coefficient of negative electrode
Warp yarnThe theoretical gram capacity of the positive electrode active material is 170mAh/g, and the theoretical gram capacity of the negative electrode active material is 372mAh/g. Wherein M pos is the molar mass of the positive electrode active material, M neg is the molar mass of the negative electrode active material, the unit is g/mol, F is Faraday constant, n is the number of electrons participating in the lithium deintercalation reaction, and C is the unit coulomb of the charge quantity.
Calculating the lithium intercalation interval of the positive electrodeNegative electrode lithium intercalation interval/>
Setting the initial interval of the lithium intercalation coefficient lower limit of the positive electrodePositive electrode lithium intercalation coefficient upper limit initial zone/>Initial interval of negative electrode lithium intercalation coefficient lower limitInitial interval of upper limit of lithium intercalation coefficient of negative electrode
Step 203: selecting a lithium intercalation coefficient group;
the method comprises the following steps: initial interval of lower limit of lithium intercalation coefficient from positive electrode Selecting any value as the lower limit/>, of the lithium intercalation coefficient of the positive electrodeInitial interval/>, from positive electrode lithium intercalation coefficient upper limitSelecting any value as the upper limit/>, of the positive electrode lithium intercalation coefficientInitial interval/>, from lower limit of lithium intercalation coefficient of negative electrodeSelecting any value as the lower limit/>, of the negative electrode lithium intercalation coefficientInitial interval/>, from upper limit of lithium intercalation coefficient of negative electrodeSelecting any value as the upper limit/>, of the lithium intercalation coefficient of the cathodeFrom the lower limit of the lithium intercalation coefficient of the positive electrode/>Positive electrode lithium intercalation coefficient upper limit/>Lower limit of lithium intercalation coefficient of negative electrode/>And the upper limit of the lithium intercalation coefficient of the negative electrode/>And forming a lithium intercalation coefficient group.
Step 204: calculating a second full cell curve;
The method comprises the following steps: lower limit of lithium intercalation coefficient from positive electrode Positive electrode lithium intercalation coefficient upper limit/>And calculating a positive state of charge/>, of the battery state of charge, SOC, in the first full-battery curveLithium intercalation coefficient lower limit/>, from negative electrodeUpper limit of lithium intercalation coefficient of negative electrode/>And calculating a negative state of charge/>, of the battery state of charge, SOC, in the first full-battery curveWhere X is the battery state of charge SOC in the first full battery curve. And calculating the positive electrode charge state SOC pos and the negative electrode charge state SOC neg corresponding to the different battery charge states SOC by taking the battery charge state SOC at any interval in the first full battery curve.
And calculating the corresponding positive electrode open circuit voltage OCV pos according to the positive electrode charge state SOC pos and the positive electrode half-cell curve. The corresponding negative open circuit voltage OCV neg is calculated from the negative state of charge SOC neg and the negative half-cell curve, and the cell open circuit voltage ocv=ocv pos-OCVneg is calculated. And obtaining a second full-battery curve corresponding to the lithium intercalation coefficient group by using the battery charge state SOC and the battery open circuit voltage OCV which are corresponding to the plurality of groups.
Step 205: calculating an error to obtain an optimal lithium intercalation coefficient;
the method comprises the following steps: a LOSS function is constructed and the function, Wherein OCV i 1 is the first open circuit voltage in the first full-cell curve, OCV i 2 is the second open circuit voltage in the second full-cell curve (i.e., the open circuit voltage of the battery calculated in step 104), n is the logarithm of the data selected for calculating the error, and i is the number of n pairs of data.
The error value at the set of lithium intercalation coefficients is determined from the LOSS function. And repeating the steps 103-105, and obtaining corresponding second full battery curves and corresponding error values when different lithium intercalation coefficient groups are obtained. Taking a group of lithium intercalation coefficients with the minimum error value as an optimal lithium intercalation coefficient group, wherein the lower limit of the positive electrode lithium intercalation coefficient in the optimal lithium intercalation coefficient groupPositive electrode lithium intercalation coefficient upper limit/>Lower limit of lithium intercalation coefficient of negative electrode/>And the upper limit of the lithium intercalation coefficient of the negative electrode/>The upper limit and the lower limit of the lithium intercalation coefficient of the positive electrode and the negative electrode of the lithium battery are obtained.
Positive electrode lithium intercalation coefficient lower limit in optimal lithium intercalation coefficient group determined through calculationPositive electrode lithium intercalation coefficient upper limit/>Lower limit of lithium intercalation coefficient of negative electrode/>Upper limit of lithium intercalation coefficient of negative electrode/>
The lower limit of the lithium intercalation coefficient of the positive electrode of the lithium battery obtained through experimentsUpper limit of lithium intercalation coefficient of positive electrodeLower limit of lithium intercalation coefficient of negative electrode/>Upper limit of lithium intercalation coefficient of negative electrode/>Fig. 9 is a schematic diagram showing the comparison of the second full cell curve and the first full cell curve at the optimal lithium intercalation coefficient set. It can also be obtained from the graph that the calculated second full cell curve substantially coincides with the true first full cell curve, and the deviation between the two is small and substantially negligible. Therefore, the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of the lithium battery, which are determined by the calculation method of the application, can be used for the performance simulation calculation of the lithium battery.
Embodiment III: referring to fig. 10 to 13, in this embodiment, a lithium iron phosphate battery is selected, and as shown in fig. 10, the positive half-cell curve is input by the user. As shown in fig. 11, is a negative half-cell curve entered by the user. As shown in fig. 12, is a full battery SOC-OCV curve entered by the user.
The calculation method of the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of the lithium iron phosphate battery comprises the following steps:
Step 301: reading user input data;
The method comprises the following steps: and reading the positive half-battery curve, the negative half-battery curve and the full-battery SOC-OCV curve input by a user, and taking the full-battery SOC-OCV curve as a first full-battery curve.
Step 302: setting an upper limit initial interval and a lower limit initial interval of a positive-negative electrode lithium intercalation coefficient;
The method comprises the following steps: setting minimum value of positive electrode lithium intercalation coefficient Maximum value of positive electrode lithium intercalation coefficientMinimum value of lithium intercalation coefficient of negative electrode/>Maximum value of lithium intercalation coefficient of negative electrode/>Positive electrode lithium intercalation intervalNegative electrode lithium intercalation interval/>
Setting the initial interval of the lithium intercalation coefficient lower limit of the positive electrodeInitial interval of positive electrode lithium intercalation coefficient upper limitInitial interval of negative electrode lithium intercalation coefficient lower limit/>Initial interval of upper limit of lithium intercalation coefficient of negative electrode
Step 303: selecting a lithium intercalation coefficient group;
the method comprises the following steps: initial interval of lower limit of lithium intercalation coefficient from positive electrode Selecting any value as the lower limit/>, of the lithium intercalation coefficient of the positive electrodeInitial interval/>, from positive electrode lithium intercalation coefficient upper limitSelecting any value as the upper limit/>, of the positive electrode lithium intercalation coefficientInitial interval/>, from lower limit of lithium intercalation coefficient of negative electrodeSelecting any value as the lower limit/>, of the negative electrode lithium intercalation coefficientInitial interval/>, from upper limit of lithium intercalation coefficient of negative electrodeSelecting any value as the upper limit/>, of the lithium intercalation coefficient of the cathodeFrom the lower limit of the lithium intercalation coefficient of the positive electrode/>Positive electrode lithium intercalation coefficient upper limit/>Lower limit of lithium intercalation coefficient of negative electrode/>And the upper limit of the lithium intercalation coefficient of the negative electrode/>And forming a lithium intercalation coefficient group.
Step 304: calculating a second full cell curve;
The method comprises the following steps: lower limit of lithium intercalation coefficient from positive electrode Positive electrode lithium intercalation coefficient upper limit/>And calculating a positive state of charge/>, of the battery state of charge, SOC, in the first full-battery curveLithium intercalation coefficient lower limit/>, from negative electrodeUpper limit of lithium intercalation coefficient of negative electrode/>And calculating a negative state of charge/>, of the battery state of charge, SOC, in the first full-battery curveWhere X is the battery state of charge SOC in the first full battery curve. And calculating the positive electrode charge state SOC pos and the negative electrode charge state SOC neg corresponding to the different battery charge states SOC by taking the battery charge state SOC at any interval in the first full battery curve.
And calculating the corresponding positive electrode open circuit voltage OCV pos according to the positive electrode charge state SOC pos and the positive electrode half-cell curve. The corresponding negative open circuit voltage OCV neg is calculated from the negative state of charge SOC neg and the negative half-cell curve, and the cell open circuit voltage ocv=ocv pos-OCVneg is calculated. And obtaining a second full-battery curve corresponding to the lithium intercalation coefficient group by using the battery charge state SOC and the battery open circuit voltage OCV which are corresponding to the plurality of groups.
Step 305: calculating an error to obtain an optimal lithium intercalation coefficient;
the method comprises the following steps: a LOSS function is constructed and the function, Wherein OCV i 1 is the first open circuit voltage in the first full-cell curve, OCV i 2 is the second open circuit voltage in the second full-cell curve (i.e., the open circuit voltage of the battery calculated in step 104), n is the logarithm of the data selected for calculating the error, and i is the number of n pairs of data.
The error value at the set of lithium intercalation coefficients is determined from the LOSS function. And repeating the steps 103-105, and obtaining corresponding second full battery curves and corresponding error values when different lithium intercalation coefficient groups are obtained. Taking a group of lithium intercalation coefficients with the minimum error value as an optimal lithium intercalation coefficient group, wherein the lower limit of the positive electrode lithium intercalation coefficient in the optimal lithium intercalation coefficient groupPositive electrode lithium intercalation coefficient upper limit/>Lower limit of lithium intercalation coefficient of negative electrode/>And the upper limit of the lithium intercalation coefficient of the negative electrode/>The upper limit and the lower limit of the lithium intercalation coefficient of the positive electrode and the negative electrode of the lithium battery are obtained.
Positive electrode lithium intercalation coefficient lower limit in optimal lithium intercalation coefficient group determined through calculationPositive electrode lithium intercalation coefficient upper limit/>Lower limit of lithium intercalation coefficient of negative electrode/>Upper limit of lithium intercalation coefficient of negative electrode/>
The lower limit of the lithium intercalation coefficient of the positive electrode of the lithium battery obtained through experimentsUpper limit of lithium intercalation coefficient of positive electrodeLower limit of lithium intercalation coefficient of negative electrode/>Upper limit of lithium intercalation coefficient of negative electrode/>Fig. 13 is a schematic diagram showing the comparison of the second full cell curve and the first full cell curve at the optimal lithium intercalation coefficient set. It can also be obtained from the graph that the calculated second full cell curve substantially coincides with the true first full cell curve, and the deviation between the two is small and substantially negligible. Therefore, the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of the lithium battery, which are determined by the calculation method of the application, can be used for the performance simulation calculation of the lithium battery.
The principles and embodiments of the present invention have been described in detail with reference to specific examples, which are provided to facilitate understanding of the method and core ideas of the present invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (10)
1. The calculation method of the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of the lithium battery is characterized by comprising the following steps:
reading an anode half-battery curve, a cathode half-battery curve and a full-battery SOC-OCV curve which are input by a user, and taking the full-battery SOC-OCV curve as a first full-battery curve;
Setting an upper limit initial interval and a lower limit initial interval of a positive electrode lithium intercalation coefficient, wherein the upper limit initial interval, the lower limit initial interval, the upper limit initial interval and the lower limit initial interval of the positive electrode lithium intercalation coefficient, the negative electrode lithium intercalation coefficient are respectively set;
the values are arbitrarily taken from each initial interval to obtain the lower limit of the lithium intercalation coefficient of the positive electrode Upper limit of lithium intercalation coefficient of positive electrodeLower limit of lithium intercalation coefficient of negative electrode/>And the upper limit of the lithium intercalation coefficient of the negative electrode/>A lithium intercalation coefficient group formed;
Calculating the state of charge of the positive electrode Negative state of chargeWherein, the positive electrode inserts lithium interval/>Negative electrode lithium intercalation intervalX is the battery state of charge SOC in the first full battery curve; calculating a corresponding positive open circuit voltage OCV pos according to the positive charge state SOC pos and the positive half-cell curve, calculating a corresponding negative open circuit voltage OCV neg according to the negative charge state SOC neg and the negative half-cell curve, and calculating a battery open circuit voltage OCV=OCV pos-OCVneg to obtain a second full-cell curve corresponding to the lithium intercalation coefficient group;
Calculating the error between the second full battery curve and the first full battery curve, changing the value in each initial interval to obtain different lithium intercalation coefficient groups, and searching the optimal lithium intercalation coefficient group corresponding to the minimum error, wherein the optimal lithium intercalation coefficient group is the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of the lithium battery.
2. The method for calculating the upper and lower limits of the positive and negative lithium intercalation coefficients of a lithium battery according to claim 1, wherein when the user sets the actual gram capacity of the positive electrode active material, the theoretical gram capacity of the positive electrode active material, the actual gram capacity of the negative electrode active material and the theoretical gram capacity of the negative electrode active material, the setting of the initial interval of the upper and lower limits of the positive and negative lithium intercalation coefficients comprises:
Calculating the lithium intercalation interval of the positive electrode Calculating a negative electrode lithium intercalation interval
Setting the initial interval of the lithium intercalation coefficient lower limit of the positive electrodePositive electrode lithium intercalation coefficient upper limit initial zone/>Initial interval of negative electrode lithium intercalation coefficient lower limit/>Initial interval of upper limit of lithium intercalation coefficient of negative electrode/> Is the minimum value of the lithium intercalation coefficient of the positive electrode in the positive electrode half-cell curve,/>Maximum value of positive electrode lithium intercalation coefficient in positive electrode half-cell curve,/>Is the minimum value of the lithium intercalation coefficient of the negative electrode in the negative electrode half-cell curve,/>The maximum value of the negative electrode lithium intercalation coefficient in the negative electrode half-cell curve is 0.5, the set degree of freedom of the negative electrode is set, and the NP ratio is the ratio of the negative electrode capacity and the positive electrode capacity of the battery.
3. The method for calculating the upper and lower limits of the positive and negative lithium intercalation coefficients of a lithium battery according to claim 2, further comprising, before setting the initial interval of the upper and lower limits of the positive and negative lithium intercalation coefficients:
Verifying data interval of positive half-cell curve input by user Whether or not to meet/>Data interval/>, of negative half-cell curve input by userWhether or not to meet/>
If yes, continuing to set an initial interval of the upper limit and the lower limit of the lithium intercalation coefficient;
and if the data do not meet the data, supplementing the positive half-cell curve and the negative half-cell curve.
4. The method for calculating the upper and lower limits of the lithium intercalation coefficient of the positive and negative electrodes of the lithium battery according to claim 1, wherein when the user sets the actual gram capacity of the positive electrode active material, the actual gram capacity of the negative electrode active material and the negative electrode active material composition, the setting of the initial interval of the upper and lower limits of the positive and negative electrode intercalation coefficient comprises:
Calculation of ，/>Wherein M pos is the molar mass of the positive electrode active material, M neg is the molar mass of the negative electrode active material, the unit is g/mol, F is Faraday constant, and n is the number of electrons participating in the deintercalation lithium reaction;
Calculating the lithium intercalation interval of the positive electrode Calculating a negative electrode lithium intercalation interval
Setting the initial interval of the lithium intercalation coefficient lower limit of the positive electrodePositive electrode lithium intercalation coefficient upper limit initial zone/>Initial interval of negative electrode lithium intercalation coefficient lower limit/>Initial interval of upper limit of lithium intercalation coefficient of negative electrode/> Is the minimum value of the lithium intercalation coefficient of the positive electrode in the positive electrode half-cell curve,/>Maximum value of positive electrode lithium intercalation coefficient in positive electrode half-cell curve,/>Is the minimum value of the lithium intercalation coefficient of the negative electrode in the negative electrode half-cell curve,/>The maximum value of the negative electrode lithium intercalation coefficient in the negative electrode half-cell curve is 0.5, the set degree of freedom of the negative electrode is set, and the NP ratio is the ratio of the negative electrode capacity and the positive electrode capacity of the battery.
5. The method for calculating the upper and lower limits of the lithium intercalation coefficient of the positive and negative electrodes of the lithium battery according to claim 1, wherein the setting the initial interval of the upper and lower limits of the lithium intercalation coefficient of the positive and negative electrodes comprises:
Setting the initial interval of the lithium intercalation coefficient lower limit of the positive electrode Positive electrode lithium intercalation coefficient upper limit initial zone/>Initial interval of negative electrode lithium intercalation coefficient lower limit/>Initial interval of upper limit of lithium intercalation coefficient of negative electrode/>
6. The method for calculating the upper and lower limits of the lithium intercalation coefficient of the positive and negative electrodes of the lithium battery according to claim 1, wherein calculating the error between the second full-battery curve and the first full-battery curve comprises:
A LOSS function is constructed and the function, Wherein, OCV i 1 is the first open-circuit voltage in the first full-cell curve, OCV i 2 is the second open-circuit voltage in the second full-cell curve, n is the data logarithm selected for calculating the error, i is the number of n pairs of data.
7. The method for calculating the upper limit and the lower limit of the lithium intercalation coefficient of the positive electrode and the negative electrode of the lithium battery according to claim 1, wherein the method adopted by the method comprises a parameter optimization algorithm or traversal, wherein the values are changed in each initial interval to obtain different lithium intercalation coefficient groups, and the optimal lithium intercalation coefficient group corresponding to the minimum error is searched.
8. An apparatus for the calculation method of the upper and lower limits of the lithium intercalation coefficient of the positive and negative electrodes of a lithium battery according to any one of claims 1 to 7, comprising:
The data acquisition unit is used for reading the positive half-battery curve, the negative half-battery curve and the full-battery SOC-OCV curve input by a user, and taking the full-battery SOC-OCV curve as a first full-battery curve;
The initial section determining unit is used for setting an upper limit initial section and a lower limit initial section of the positive and negative electrode lithium intercalation coefficient, and comprises setting an upper limit initial section, a lower limit initial section, an upper limit initial section and a lower limit initial section of the positive and negative electrode lithium intercalation coefficient respectively;
a lithium intercalation coefficient group selecting unit for arbitrarily selecting values from each initial interval to obtain the lower limit of the lithium intercalation coefficient of the positive electrode Positive electrode lithium intercalation coefficient upper limit/>Lower limit of lithium intercalation coefficient of negative electrode/>And the upper limit of the lithium intercalation coefficient of the negative electrode/>A lithium intercalation coefficient group formed;
A data calculation unit for calculating the state of charge of the positive electrode Negative state of chargeWherein, the positive electrode inserts lithium interval/>Negative electrode lithium intercalation intervalX is the battery state of charge SOC in the first full battery curve; calculating a corresponding positive open circuit voltage OCV pos according to the positive charge state SOC pos and the positive half-cell curve, calculating a corresponding negative open circuit voltage OCV neg according to the negative charge state SOC neg and the negative half-cell curve, and calculating a battery open circuit voltage OCV=OCV pos-OCVneg to obtain a second full-cell curve corresponding to the lithium intercalation coefficient group;
And the error comparison unit is used for calculating the error between the second full battery curve and the first full battery curve, changing the value in each initial interval to obtain different lithium intercalation coefficient groups, and searching the optimal lithium intercalation coefficient group corresponding to the minimum error, wherein the optimal lithium intercalation coefficient group is the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of the lithium battery.
9. An electronic device, characterized in that the electronic device comprises a memory and a processor, at least one program instruction is stored in the memory, and the processor is used for realizing the calculation method of the upper limit and the lower limit of the lithium intercalation coefficient of the anode and the cathode of the lithium battery according to any one of claims 1 to 7 by loading and executing the at least one program instruction.
10. A computer storage medium, wherein at least one program instruction is stored in the computer storage medium, and the at least one program instruction is loaded and executed by a processor to implement the method for calculating the upper limit and the lower limit of the lithium intercalation coefficient of the positive electrode and the negative electrode of the lithium battery according to any one of claims 1 to 7.
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