Method for detecting charging performance of three-electrode battery cell and method for comparing charging capacities of different battery cells
By performing linear fitting and polynomial differentiation of the charging rate and negative electrode potential at the same temperature, the charging capacity of the three-electrode battery cell is calculated, which solves the problem of unenergized calculation of the charging capacity in the prior art, and realizes charging of the battery cell Accurate evaluation and comparison of capabilities reduces assessment costs and verifies the reliability of the method.
Patent Information
- Application Number
- CN202411369045.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-29
- Publication Date
- 2024-12-24
AI Technical Summary
The prior art has failed to effectively quantify the charging capacity of three-electrode batteries at different SOCs and temperatures, and cannot accurately compare the charging performance of different batteries.
By uniformly selecting multiple charging rate values at the same temperature for charging, recording the negative electrode potential, and using linear fitting and polynomial differentiation, the time required to charge to 100% SOC at the 0mv safe negative electrode potential is calculated, and the battery cell's Charging rate and charging capability.
Accurate quantification and comparison of the charging capacity of the battery cell is realized, and can intuitively reflect the full SOC charging capacity of the battery cell, reduce the evaluation cost, and demonstrate the reliability of the method through verification.
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Figure CN119179004A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of battery detection, and in particular to a method for detecting charging performance of a three-electrode battery cell and a method for comparing charging capacities of different battery cells. Background Art
[0002] CN113937340A and CN 118299769 A prepare and improve three-electrode batteries through different methods, making three-electrode cells have a wide range of applications. Patent CN117728055 A uses three electrodes to improve the lithium deposition of batteries under specific charging conditions, and formulates a method and application for fast charging without lithium deposition, but does not quantitatively calculate the charging capacity of different cells at different temperatures under full SOC.
[0003] In view of this, the present invention is proposed. Summary of the invention
[0004] The object of the present invention is to provide a method for detecting the charging performance of a three-electrode battery cell and a method for comparing the charging capabilities of different battery cells.
[0005] The present invention is achieved in that:
[0006] In a first aspect, an embodiment of the present invention provides a method for detecting charging performance of a three-electrode battery cell, comprising:
[0007] Step A: At the same temperature, within the allowable charging rate range, multiple charging rate values are uniformly selected for multiple groups of charging, each group is charged to the same target SOC value, and the corresponding negative electrode potential is recorded when charging to the target SOC value. The obtained data is linearly fitted to obtain the linear relationship between the charging rate and the negative electrode potential at the target SOC value 1: y1=k*x1+b, where x1 is the charging rate and y1 is the negative electrode potential;
[0008] Step B: uniformly select multiple SOC values in the entire SOC range as target SOC values, and obtain equation 1 at multiple different SOC values in the same manner as in step A;
[0009] Step C: Let the value of y1 in the relational expression 1 under multiple different SOC values be 0, and calculate the charging rate value of the negative electrode potential of 0mv under different SOC values;
[0010] Step D: Fit the charge rate value of the 0mv negative electrode potential under different SOC values to obtain polynomial 2: y = A1*x 3 +A2*x 2 +A3*x+A, where y is the charging rate value and x is the SOC value;
[0011] Step E: Differentiate Polynomial 2 Calculate the time required to charge to 100% SOC at 0mv safe negative electrode potential.
[0012] In an optional embodiment, by The full SOC charging equivalent rate is calculated.
[0013] In an optional embodiment, steps A to E are performed at different temperatures to obtain the time required to charge to 100% SOC at a 0 mv safety negative electrode potential at different temperatures, or to obtain the full SOC charging equivalent rate.
[0014] In an alternative embodiment, the different temperatures range from 0 to 55°C.
[0015] In an optional implementation, in step B, multiple SOC values are uniformly selected within the SOC range of 10% to 90% as the target SOC value.
[0016] In an optional embodiment, the three-electrode battery cell is energy-based, and the allowable charging rate range is 0.1 to 2C;
[0017] Alternatively, the three-electrode battery cell is a power type, and the allowable charging rate range is 1 to 5C.
[0018] In a second aspect, an embodiment of the present invention provides a method for comparing charging capabilities of different three-electrode cells, including:
[0019] The charging performance of each three-electrode battery cell is tested according to the aforementioned testing method to obtain the time required for each three-electrode battery cell to be charged to 100% SOC at a 0mv safety negative electrode potential;
[0020] Compare the time required for different three-electrode cells to charge to 100% SOC at 0mv safe negative electrode potential;
[0021] Compare the time required for different three-electrode cells to charge to 100% SOC at 0mv safe negative electrode potential. The smaller the value, the higher the charging capacity, and vice versa.
[0022] The present invention has the following beneficial effects:
[0023] The charging capacity detection method provided by the present invention studies the relationship between the charging rate, the negative electrode potential and the SOC, and uses linear fitting to obtain a linear relationship 1 between the charging rate and the negative electrode potential. The relationship 1 is used to obtain a polynomial 2 of the charging rate value of the 0mv negative electrode potential under different SOC values. The time required to charge to 100% SOC under the 0mv safe negative electrode potential can be calculated by differentiating the polynomial 2. The charging capacity can be judged according to the time value. The shorter the time value, the higher the charging capacity, and vice versa. The detection method provided by the present invention can quantify the equivalent charging rate of the battery cell, and can intuitively reflect the full SOC charging capacity of the battery cell. After verification, the detection method is reliable. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.
[0025] Figure 1 This is a curve diagram of the polynomial fitted in Example 1;
[0026] Figure 2 This is a comparison chart of charging capabilities at different temperatures between Example 1 and Example 2;
[0027] Figure 3 This is a comparison chart of the charging capabilities of different types of batteries in Examples 1, 3 and 4. DETAILED DESCRIPTION
[0028] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.
[0029] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.
[0030] An embodiment of the present invention provides a method for detecting charging performance of a three-electrode battery cell, comprising:
[0031] Step A: At the same temperature, within the allowable charging rate range, multiple charging rate values are uniformly selected for multiple groups of charging, each group is charged to the same target SOC value, and the corresponding negative electrode potential is recorded when charging to the target SOC value. The obtained data is linearly fitted to obtain the linear relationship between the charging rate and the negative electrode potential at the target SOC value 1: y1=k*x1+b, where x1 is the charging rate and y1 is the negative electrode potential;
[0032] Step B: uniformly select multiple SOC values in the entire SOC range as target SOC values, and obtain equation 1 at multiple different SOC values in the same manner as in step A;
[0033] Step C: Let the Y value in the relational expression 1 under multiple different SOC values be 0, and calculate the charging rate value of the negative electrode potential of 0mv under different SOC values;
[0034] Step D: Fit the charge rate value of the 0mv negative electrode potential under different SOC values to obtain polynomial 2: y = A1*x 3 +A2*x 2 +A3*x+A, where y is the charging rate value and x is the SOC value;
[0035] Step E: Differentiate Polynomial 2 Calculate the time required to charge to 100% SOC at 0mv safe negative electrode potential.
[0036] The charging capacity detection method provided by the present invention studies the relationship between the charging rate, the negative electrode potential and the SOC, and uses linear fitting to obtain a linear relationship 1 between the charging rate and the negative electrode potential. The relationship 1 is used to obtain a polynomial 2 of the charging rate value of the 0mv negative electrode potential under different SOC values. The time required to charge to 100% SOC under the 0mv safe negative electrode potential can be calculated by differentiating the polynomial 2. The charging capacity can be judged according to the time value. The shorter the time value, the higher the charging capacity, and vice versa. The detection method provided by the present invention can quantify the equivalent charging rate of the battery cell and can intuitively reflect the full SOC charging capacity of the battery cell.
[0037] Optionally, by The full SOC charging equivalent rate is calculated.
[0038] By comparing the full SOC charging equivalent rate, the larger the C value, the higher the charging capacity, and vice versa.
[0039] Optionally, steps A to E are performed at different temperatures to obtain the time required to charge to 100% SOC at a safe negative electrode potential of 0 mv at different temperatures, or to obtain the full SOC charging equivalent rate.
[0040] By testing at different temperatures, the charging capacity of the same battery cell at different temperatures can be obtained.
[0041] Optionally, the range of different temperatures is 0-55°C. The above temperature range is a relatively common working environment temperature range. It should be noted that if the charging capacity of the battery cell in an extreme temperature environment is to be tested, the test can also be set at the corresponding extreme temperature.
[0042] Optionally, in step B, multiple SOC values are uniformly selected within the SOC range of 10% to 90% as the target SOC value, for example, 10%, 20% ... 90%.
[0043] Optionally, the three-electrode battery cell is energy-based, and the allowable charging rate range is 0.1 to 2C;
[0044] Alternatively, the three-electrode battery cell is a power type, and the allowable charging rate range is 1 to 5C.
[0045] The embodiment of the present invention further provides a method for comparing charging capabilities of different three-electrode cells, including:
[0046] The charging performance of each three-electrode battery cell is tested according to the testing method provided by the present invention to obtain the time required for each three-electrode battery cell to be charged to 100% SOC at a 0mv safety negative electrode potential;
[0047] Compare the time required for different three-electrode cells to charge to 100% SOC at 0mv safe negative electrode potential. The smaller the value, the higher the charging capacity, and vice versa.
[0048] Example 1
[0049] Provide 3 fresh A1 three-electrode cells and test their charging capacity at 25°C. Specifically:
[0050] The target charging SOC is selected as 10% SOC, 20% SOC, 30% SOC, 40% SOC, 50% SOC, 60% SOC, 70% SOC, 80% SOC, and 90% SOC;
[0051] The battery was charged at rates of 0.5C, 0.8C, 1C, 1.2C and 1.5C to the target charging SOC, and the negative electrode potential was measured when the battery was charged at different rates to the target SOC value.
[0052] Multiple relationships are obtained by fitting:
[0053] 10% SOC: y1=-0.0389*x1+0.1871;
[0054] 20% SOC: y1=-0.0321*x1+0.136;
[0055] 30% SOC: y1=-0.0253*x1+0.1119;
[0056] 40% SOC: y1=-0.0275*x1+0.1092;
[0057] 50% SOC: y1=-0.0290*x1+0.1029;
[0058] 60% SOC: y1=-0.0241*x1+0.0859;
[0059] 70% SOC: y1=-0.0238*x1+0.0777;
[0060] 80% SOC: y1=-0.0276*x1+0.0757;
[0061] 90% SOC: y1=-0.0338*x1+0.0718;
[0062] Let the value of y1 in the above multiple relationship be 0, and obtain the charging rate value of 0mv negative electrode potential under different SOC values;
[0063] 10%SOC:4.81;
[0064] 20%SOC:4.23;
[0065] 30%SOC:4.42;
[0066] 40%SOC: 3.97;
[0067] 50%SOC: 3.55;
[0068] 60%SOC:3.56;
[0069] 70% SOC: 3.27;
[0070] 80% SOC: 2.74;
[0071] 90%SOC:2.12.
[0072] Through the above multiple sets of data, the polynomial is fitted: y = -6.1448*x 3 +7.1866*x 2 -4.8323*x+5.161, such as Figure 1 shown.
[0073] By integrating the polynomial, we can get The calculated t is 0.3039h; The calculated C is 3.2902.
[0074] Example 2
[0075] Three fresh three-electrode cells of the same model as that used in Example 1 were provided, and their charging capacity was measured at 20° C., specifically:
[0076] The target charging SOC is selected as 10% SOC, 20% SOC, 30% SOC, 40% SOC, 50% SOC, 60% SOC, 70% SOC, 80% SOC, and 90% SOC;
[0077] The battery was charged at rates of 0.5C, 0.8C, 1C, 1.2C and 1.5C to the target charging SOC, and the negative electrode potential was measured when the battery was charged at different rates to the target SOC value.
[0078] Multiple relationships are obtained by fitting:
[0079] 10% SOC: y1=-0.0575*x1+0.1860;
[0080] 20% SOC: y1=-0.0397*x1+0.1307;
[0081] 30% SOC: y1=-0.0268*x1+0.1040;
[0082] 40% SOC: y1=-0.0270*x1+0.0991;
[0083] 50% SOC: y1=-0.0249*x1+0.0890;
[0084] 60% SOC: y1=-0.0216*x1+0.0759;
[0085] 70% SOC: y1=-0.0230*x1+0.0697;
[0086] 80% SOC: y1=-0.0266*x1+0.0649;
[0087] 90% SOC: y1=-0.0371*x1+0.0603.
[0088] Let the value of y1 in the above multiple relationship be 0, and obtain the charging rate value of 0mv negative electrode potential under different SOC values;
[0089] 10% SOC: 3.23;
[0090] 20% SOC: 3.29;
[0091] 30% SOC: 3.88;
[0092] 40%SOC: 3.67;
[0093] 50%SOC: 3.57;
[0094] 60%SOC:3.51;
[0095] 70%SOC:3.03;
[0096] 80% SOC: 2.44;
[0097] 90%SOC:1.63.
[0098] Through the above multiple sets of data, the polynomial is fitted: y = -13.725*x 3 +19.015*x 2 -9.8555*x+5.1783.
[0099] By integrating the polynomial, we can get The calculated t is 0.3711h; The calculated C is 2.6944.
[0100] Comparing the charging capabilities of Example 1 and Example 2, the C value of Example 1 is larger than the C value of Example 2, indicating that the A1 battery has a higher charging capability at 25°C.
[0101] Example 3
[0102] Provide 3 fresh A2 three-electrode cells and test their charging capacity at 25°C. Specifically:
[0103] The target charging SOC is selected as 10% SOC, 20% SOC, 30% SOC, 40% SOC, 50% SOC, 60% SOC, 70% SOC, 80% SOC, and 90% SOC;
[0104] The battery was charged at 0.5C, 0.8C, 1C, 1.2C and 1.5C rates to the target SOC, and the negative electrode potential was measured when the battery was charged at different rates to the target SOC value.
[0105] Multiple relationships are obtained by fitting:
[0106] 10% SOC: y1=-0.0412*x1+0.1906;
[0107] 20% SOC: y1=-0.0374*x1+0.1426;
[0108] 30% SOC: y1=-0.0280*x1+0.1126;
[0109] 40% SOC: y1=-0.0307*x1+0.1098;
[0110] 50% SOC: y1=-0.0317*x1+0.1035;
[0111] 60% SOC: y1=-0.0266*x1+0.0884;
[0112] 70% SOC: y1=-0.0254*x1+0.0792;
[0113] 80% SOC: y1=-0.0292*x1+0.0759;
[0114] 90% SOC: y1=-0.0334*x1+0.0695.
[0115] Let the value of y1 in the above multiple relationship be 0, and obtain the charging rate value of 0mv negative electrode potential under different SOC values;
[0116] 10%SOC:4.63;
[0117] 20% SOC: 3.81;
[0118] 30%SOC:4.02;
[0119] 40%SOC: 3.58;
[0120] 50% SOC: 3.27;
[0121] 60%SOC: 3.32;
[0122] 70%SOC: 3.12;
[0123] 80%SOC: 2.60;
[0124] 90%SOC:2.08.
[0125] Through the above multiple sets of data, the polynomial is fitted: y = -11.0424*x 3 +15.8026*x 2 -8.8648*x+5.2932.
[0126] By integrating the polynomial, we can get The calculated t is 0.3255h; The calculated C is 3.0722.
[0127] Example 4
[0128] Provide 3 fresh A3 three-electrode cells and test their charging capacity at 25°C. Specifically:
[0129] The target charging SOC is selected as 10% SOC, 20% SOC, 30% SOC, 40% SOC, 50% SOC, 60% SOC, 70% SOC, 80% SOC, and 90% SOC;
[0130] The battery was charged at rates of 0.5C, 0.8C, 1C, 1.2C and 1.5C to the target charging SOC, and the negative electrode potential was measured when the battery was charged at different rates to the target SOC value.
[0131] 10% SOC: y1=-0.0390*x1+0.1898;
[0132] 20% SOC: y1=-0.0357*x1+0.1428;
[0133] 30% SOC: y1=-0.0344*x1+0.1208;
[0134] 40% SOC: y1=-0.0420*x1+0.1212;
[0135] 50% SOC: y1=-0.0452*x1+0.1162;
[0136] 60% SOC: y1=-0.0450*x1+0.1067;
[0137] 70% SOC: y1=-0.0483*x1+0.1022;
[0138] 80% SOC: y1=-0.0558*x1+0.1040;
[0139] 90% SOC: y1=-0.0709*x1+0.1119.
[0140] Let the value of y1 in the above multiple relationship be 0, and obtain the charging rate value of 0mv negative electrode potential under different SOC values;
[0141] 10% SOC: 4.87;
[0142] 20%SOC:4.00;
[0143] 30%SOC: 3.51;
[0144] 40%SOC: 2.89;
[0145] 50%SOC: 2.57;
[0146] 60%SOC:2.37;
[0147] 70% SOC: 2.12;
[0148] 80% SOC: 1.86;
[0149] 90%SOC:1.58.
[0150] Through the above multiple sets of data, the polynomial is fitted: y = -6.3298*x 3 +13.3130*x 2 -11.6136&*x+5.8785.
[0151] By integrating the polynomial, we can get The calculated t is 0.4000h; The calculated C is 2.5005.
[0152] Experimental Example 1
[0153] Figure 2 , Figure 3 It can be seen that this calculation method can quantitatively calculate the charging capacity of different types of battery cells at the same temperature and the same type of battery cells at different temperatures under full SOC.
[0154] Comparing the C values calculated in Example 1, Example 3 and Example 4, the C values are 3.2902, 3.0722 and 2.5005, respectively. By comparing according to the method provided in the embodiment of the present invention, it is concluded that the room temperature charging capacities of the three batteries are A1>A2>A3, respectively, from high to low.
[0155] Experimental Example 2
[0156] This experimental example is used to verify the reliability of the method provided by the embodiment of the present invention.
[0157] Since the maximum charging current allowed by the battery cell is a critical value, the stacked battery cell with multiple electrode sheets is usually cycled at the maximum allowed charging current. After the test, the battery cell is disassembled and it can be observed that the lithium deposition of multiple electrode sheets in each battery cell is partially lithium deposited and partially not. Based on this principle, the following experimental design is performed:
[0158] Take 10 cells identical to A1, A2 and A3 respectively, and use the C values (3.2902C, 3.0722C, 2.5005C) calculated in Example 1, Example 3 and Example 4 as the maximum charging current value for charging at 25°C, discharging at 1C, and a charge and discharge standby time of 0.5h for a cycle test. After 100 cycles, the cells are disassembled, and the number of lithium-deposited pole pieces in each cell is recorded, and the lithium-deposited pole piece ratio is recorded in Table 1.
[0159] Table 1 Lithium deposition on the electrode after each battery cycle
[0160] Group Example 1 Example 3 Example 4 Battery 1 4% 8% 0% Battery 2 0% 18% 16% Battery 3 12% 11% 25% Battery 4 4% 3% 4% Battery 5 28% 5% 11% Battery 6 16% 13% 29% Battery 7 4% 11% 21% Battery Cell 8 7% 21% 4% Battery 9 0% 0% 7% Battery 10 12% 0% 0%
[0161] Note: If the proportion exceeds 10%, it is considered that the battery cell has lithium deposition, and if it is less than 10%, it is considered that the battery cell has basically no lithium deposition.
[0162] It can be seen from Table 1 that among the 10 cells of Example 1 (A1), 6 cells have basically no lithium deposition, 4 cells have lithium deposition, and the number of cells with lithium deposition accounts for 40% of the total number of cells tested, which does not exceed 80%, indicating that charging at 3.2902C is already a critical value for charging. It can be expected that if charging is higher than this value, the proportion of lithium deposition electrodes will increase to more than 10%, and the number of cells with lithium deposition will be greater;
[0163] Among the 10 cells in Example 3 (A2), 5 cells have basically no lithium deposition, and 5 cells have lithium deposition. The number of cells with lithium deposition accounts for less than 80% of the total number of cells tested, indicating that charging at 3.0722C is already a critical charging value. It can be expected that if charged at a value higher than this, the proportion of lithium deposition electrodes will increase to more than 10%, and the number of cells with lithium deposition will be greater.
[0164] Among the 10 battery cells in Example 4 (A3), 5 battery cells have basically no lithium deposition, and 5 battery cells have lithium deposition. The number of battery cells with lithium deposition accounts for less than 80% of the total number of test battery cells, indicating that charging at 2.5005C is already the critical charging value. It can be expected that if charging is higher than this value, the proportion of lithium deposition electrodes will increase to more than 10%, and the number of battery cells with lithium deposition will be even greater.
[0165] It can be seen from the above results that the maximum charging capacity value (full SOC charging equivalent rate) obtained by the method provided in the embodiment of the present invention is effective.
[0166] From the disassembly results of a large number of test cells in various embodiments after 100 cycles, it can be seen that the charging capacity calculated by the calculation method of this scheme is close to the actual maximum charging capacity of the cell, which can verify the feasibility of the method provided by the present invention.
[0167] In summary, the charging capacity detection method provided by the present invention can quantify the equivalent charging rate of the battery cell. There is no need to judge the charging capacity through a large number of tests and battery cell disassembly, which reduces the cost of evaluating the battery cell charging capacity. It can intuitively reflect the full SOC charging capacity of the battery cell, and it has been verified that the method is reliable.
[0168] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims
1. A method for detecting charging performance of a three-electrode battery cell, characterized in that: include: Step A: At the same temperature, within the allowable charging rate range, multiple charging rate values are uniformly selected for multiple groups of charging, each group is charged to the same target SOC value, and the corresponding negative electrode potential is recorded when charging to the target SOC value. The obtained data is linearly fitted to obtain the linear relationship between the charging rate and the negative electrode potential at the target SOC value 1: y1=k*x1+b, where x1 is the charging rate and y1 is the negative electrode potential; Step B: uniformly selecting multiple SOC values in the entire SOC range as the target SOC value, and obtaining the relationship 1 under multiple different SOC values in the manner of step A; Step C: Let the value of y1 in the relational expression 1 under multiple different SOC values be 0, and calculate the charging rate value of the negative electrode potential of 0mv under different SOC values; Step D: Fit the charge rate value of the 0mv negative electrode potential under different SOC values to obtain polynomial 2: y = A1*x 3 +A2*x 2 +A3*x+A, where y is the charging rate value and x is the SOC value; Step E: Differentiate the polynomial 2 Calculate the time required to charge to 100% SOC at 0mv safe negative electrode potential.
2. The detection method according to claim 1, characterized in that: Depend on The full SOC charging equivalent rate is calculated.
3. The detection method according to claim 2, characterized in that: Steps A to E are performed at different temperatures to obtain the time required for charging to 100% SOC at a 0mv safety negative electrode potential at different temperatures, or to obtain the full SOC charging equivalent rate.
4. The detection method according to claim 3, characterized in that: The different temperatures range from 0 to 55°C.
5. The detection method according to claim 1, characterized in that: In the step B, a plurality of SOC values are uniformly selected within the range of 10% to 90% SOC as the target SOC value.
6. The detection method according to claim 1, characterized in that: The three-electrode battery cell is energy-based, and the allowable charging rate range is 0.1 to 2C; Alternatively, the three-electrode battery cell is a power type, and the allowable charging rate range is 1 to 5C.
7. A method for comparing the charging capabilities of different three-electrode cells, characterized in that: include: Testing the charging performance of each three-electrode battery cell according to the testing method according to any one of claims 1 to 5, and obtaining the time required for each three-electrode battery cell to be charged to 100% SOC at a 0mv safety negative electrode potential; Compare the time required for different three-electrode cells to charge to 100% SOC at 0mv safe negative electrode potential. The smaller the value, the higher the charging capacity, and vice versa.
Citation Information
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