CN102088107A - Cell die and method for rapid evaluating cell matching degree - Google Patents
Cell die and method for rapid evaluating cell matching degree Download PDFInfo
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- CN102088107A CN102088107A CN2010106042230A CN201010604223A CN102088107A CN 102088107 A CN102088107 A CN 102088107A CN 2010106042230 A CN2010106042230 A CN 2010106042230A CN 201010604223 A CN201010604223 A CN 201010604223A CN 102088107 A CN102088107 A CN 102088107A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a cell die and a method for rapid evaluating cell matching degree. The method is characterized by using a specified die to prepare simulated cells or half cells, utilizing a simplified Arrhenius empirical formula to test and compute the reaction activation energy when different pole pieces are combined in a specified temperature range, and establishing a standard for judging the pole matching degree according to the reaction activation energy so as to evaluate the performance of relevant poles effectively. The method is applicable to pole pieces prepared from anode material and cathode material of various lithium ion batteries, can be widely applied to process evaluation, raw material evaluation and the like, has simple procedures, is easy to operate, has rapid and accurate data, and effectively reduces the material cost and time cost in relevant work. The invention also provides a cell die which is easy to assemble, has high accuracy and can be used repeatedly.
Description
Technical field
The present invention relates to a kind of battery mould, the mould that especially a kind of battery testing uses.The invention still further relates to a kind of method of testing of battery, especially a kind of method of quick evaluation battery matching degree.
Background technology
The environmental protection lithium rechargeable battery is used widely in portable type electronic product, communication tool, electric tool in recent years, and progressively becomes the electrical source of power of electric automobile.For the performance requirement of continuous lifting, the good raw material and the production technology of optimization are more and more paid close attention to.In general experiment is produced, the quality of assessment battery design scheme or pole piece technology, what mainly use is to make battery, the method for test battery performance is determined the quality of technology and the quality of pole piece technology by every battery performance parameter that contrast records.There is tangible drawback in this method: the cycle is long, and it is big to expend inventory, for time cost and material cost bigger waste is arranged all.
Activation energy is the notion that Sweden scientist Arrhenius (Arrhenius) proposes the earliest before 1889, and it has great importance in chemistry.With regard to its definition and essence, different researchers is disagreed.But have a bit to have obtained common recognition: activation energy can effectively characterize the complexity that chemical reaction takes place.Activation energy is big more, and potential barrier is high more, reacts difficult more generation.
Utilize this characteristic of activation energy, a lot of fields utilize apparent activation energy to estimate the complexity of specific reaction.In the battery charge and discharge process, topmost process is the electrochemical reaction of active material.This process has corresponding with it activation energy.The related work that utilizes this activation energy to estimate the battery system quality does not have disclosed report as yet.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of battery mould, and a kind of method of quick evaluation battery matching degree, can estimate battery positive/negative plate matching degree, raw material and pole piece performance fast, and it is simple to operate, data are accurate, a large amount of saving material, time, human cost.
For solving the problems of the technologies described above, the technical scheme of battery mould of the present invention is, the middle part that comprises tubular, with the end that is arranged on two ends, described tubular middle part, described end is provided with the lug boss that cooperates with this through hole corresponding to the position of described middle part axially extending bore, and after the assembling, described lug boss is clipped in the simulated battery in the mould in the through hole at described middle part, described end is provided with the lug that connects of drawing lead, and described two ends are the conducting by mould self not.
The present invention also provides a kind of method of quick evaluation battery matching degree, its technical scheme is, use above-mentioned mould to prepare simulated battery, utilize AC impedence method to measure electrochemical reaction resistance R ct under the simulated battery different temperatures of various combination by the lead-in wire that connects lug, calculate reaction activity by the Arrhenius empirical equation, determine the degree of different batteries couplings by comparison activation energy value: when activation energy numerical value is low more, the battery matching degree is good more; When activation energy numerical value is high more, the battery matching degree is poor more.
The present invention passes through technique scheme, can estimate battery positive/negative plate matching degree, raw material and pole piece performance fast, and it is simple to operate, data are accurate, simultaneously a large amount of savings material, time, human cost, compared to common method in the industry remarkable advantages is arranged, great Practical significance is arranged for auxiliary pole piece, battery design.
Description of drawings
Below in conjunction with drawings and Examples the present invention is carried out further detailed description.
Fig. 1 is the schematic diagram of battery mould medial end portions of the present invention.
Fig. 2 is the schematic diagram at middle part in the battery mould of the present invention.
Fig. 3 is the schematic diagram of battery mould assembling of the present invention.
Fig. 4 is the profile of battery mould assembling of the present invention.
Fig. 5 by the present invention according to embodiment 1 the AC impedance (Rct) of survey battery under different temperatures (T), with
With
Variation diagram.
Fig. 6 by the present invention according to embodiment 2 the AC impedance (Rct) of survey battery under different temperatures (T), with
With
Variation diagram.
Wherein Reference numeral is, 1. the end; 2. middle part; 3. end; 4. spring; 5. connect lug.
Embodiment
The invention provides a kind of battery mould, as Fig. 1-shown in Figure 4, the middle part 2 that comprises tubular, with the end 1 and 3 that is arranged on 2 two ends, described tubular middle part, described end 1 and 3 positions corresponding to described middle part axially extending bore are provided with the lug boss that cooperates with this through hole, and after the assembling, described lug boss is clipped in the simulated battery in the mould in the through hole at described middle part, described end be provided with draw lead connect lug 5, described two ends 1 and 3 are the conducting by mould self.
Described lug boss is provided with external screw thread, and described through hole is provided with corresponding internal thread, and described lug boss and described through hole make described end be connected with described middle part by rotation by threads engaged.
Silica gel sealing ring and polytetrafluoroethylene film sealing are used in the junction of described middle part and end.
Described lug boss is provided with spring 4, and described spring 4 closely contacts the positive/negative plate of simulated battery.
The material of described end is one or more of iron, copper, aluminium and metal thereof, non-metal alloy, and the material at described middle part is polytetrafluoroethylene, nylon, polymethyl methacrylate or PP.
The invention also discloses a kind of method of quick evaluation battery matching degree, use above-mentioned mould to prepare simulated battery, utilize AC impedence method to measure electrochemical reaction resistance R ct under the simulated battery different temperatures of various combination by the lead-in wire that connects lug, calculate reaction activity by the Arrhenius empirical equation, determine the degree of different batteries couplings by comparison activation energy value: when activation energy numerical value is low more, the battery matching degree is good more; When activation energy numerical value is high more, the battery matching degree is poor more.
Described AC impedence method comprises the steps:
Simulated battery is carried out charge and discharge cycles 3 times, and multiplying power is 0.2C, is used for activation;
Simulated battery after the activation is carried out the test of electrochemical AC impedance spectrum, amplitude is 1 to 50mV, high frequency frequency 1KHz to 1MHz, low frequency frequency 0.00001Hz to 10Hz, test is appointed in-20 ℃ to 100 ℃ temperature ranges and is got 3 to 100 temperature spots and carry out repetition, obtains electrochemical reaction resistance R ct by The Fitting Calculation;
Utilize the Arrhenius empirical equation after simplifying
With
Right
Mapping is tried to achieve reaction activity by slope, and wherein, A is a pre-exponential factor, can be in the hope of lnA according to intercept among the figure.Because activation energy Ea is only by in the Arrhenius empirical equation
Slope decision, so lnA is to not influence of activation energy.
The positive pole of described simulated battery is including but not limited in LiFePO4, cobalt acid lithium, LiMn2O4, nickel cobalt manganese, the nickel cobalt aluminium commercialization lithium ion secondary battery anode material one or more, and negative pole is including but not limited in native graphite, Delanium, silicon, the metal oxide negative material one or more.
Described simulated battery is the half-cell of metal lithium sheet for specifying the negative or positive electrode sheet to electrode.
When activation energy was less than or equal to 30, the battery matching degree was good; When activation energy greater than 30 less than 40 the time, the battery matching degree is qualified; When activation energy more than or equal to 40 the time, the battery matching degree is defective.
The present invention will be described in more detail below by concrete case study on implementation.
1, assembling simulated battery: use special-purpose mould, this mould compare with traditional battery assembling mould has simple fast, characteristics such as simulated battery rate of finished products height, simultaneously accurate in order to guarantee data, what guarantee to use in the control experiment is electrolyte of the same race and barrier film.
2, simulated battery is carried out charge and discharge cycles 3 times, multiplying power is 0.2C, is used for activation.
3, the simulated battery after the activation carries out electrochemical AC impedance spectrum (EIS) test, and amplitude is 1 to 50mV, high frequency frequency 1KHz to 1MHz, low frequency frequency 0.00001Hz to 10Hz.Test is appointed in-20 ℃ to 100 ℃ temperature ranges and is got 3 to 100 temperature spots and carry out repetition.Obtain electrochemical reaction resistance R ct by The Fitting Calculation.
4, Arrhenius experience (Arrhenius) formula after utilization is simplified
With
Right
Mapping is tried to achieve reaction activity by slope.
5, the present invention has determined comparison standard at the different activities material by a large amount of experiments, accurately and reliably.
(1) making of positive plate
Coat uniformly on the aluminium foil as the anode sizing agent that will use LiFePO 4 material, through 125 ℃ of dryings 1 hour, calendering then was cut into diameter and is 20 millimeters positive plate, contains the 20mg positive active material in each positive plate.Use the slurry of four kinds of different proportionings and technology to prepare pole piece A, B, E, F by above-mentioned steps.
(2) making of negative plate
In the cathode size coating uniformly and Copper Foil that will use Delanium, at the pressure lower sheeting of 2 MPas, 300 ℃ of heat treatment is 24 hours under condition of nitrogen gas, then calendering, cut into the negative plate of 21 millimeters of diameters, contain the 15mg negative active core-shell material in each negative plate.Use the slurry of two kinds of different proportionings and technology to prepare pole piece C, D by above-mentioned steps.
(3) making of battery
The polypropylene diaphragm and the cathode pole piece of above-mentioned anode pole piece, 25 micron thickness are overlapped into electric core successively, in the Analog battery die of packing into, electrolyte are injected simulated battery with the amount of 3.8g/Ah, simulated battery is made in sealing.Electrolyte all uses ternary electrolyte of the same race, and barrier film is three layers of barrier film of the thick PP/PE/PP of the 25um of celgard.
Adopt the method identical and the step preparation is anodal, negative pole and battery with embodiment 1, the anodal pole piece A that uses, negative pole uses pole piece C, and battery is numbered 1#.
Adopt method and the step identical with embodiment 2 to prepare battery, different is that negative pole is D, and battery is numbered 2#.
Adopt method and the step identical to prepare battery with embodiment 2, different is B just very, battery is numbered 3#.
Employing prepares battery with embodiment 4 identical method and steps, and different is that negative pole is D, and battery is numbered 4#.
Adopt method and the step identical to prepare battery with embodiment 2, different is E just very, negative pole is that diameter is the metal lithium sheet of 21mm, battery is numbered 5#.
Embodiment 7
Adopt method and the step identical with embodiment 6 to prepare battery, different is that positive plate is pole piece F, and battery is numbered 6#.
Performance test
1. ac impedance measurement
The ac impedance spectroscopy of four simulated batteries when 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ 5 temperature spots among the difference test implementation example 1-4, match obtains four the electrochemical reaction resistance R cts of battery under different temperatures.Calculate
Value, data such as following table 1.
Table 1
The ac impedance spectroscopy of two simulated batteries when 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ 5 temperature spots among the difference test implementation example 5-6, match obtains four the electrochemical reaction resistance R cts of battery under different temperatures.Calculate
Value, data such as following table 2.
Table 2
2. activation energy calculates
According to data in the table 1, with
Right
Mapping is near linear as shown in Figure 5, obtains the slope of straight line by match, and this value is reaction activity Ea.According to shown in Figure 5, embodiment 1 cell activation can be 45.09, and embodiment 2 cell activation can be 38.24, and embodiment 3 cell activation can be 39.05, and embodiment 4 cell activation can be 21.44.By the comparison standard scale as can be seen, embodiment 1 battery is defective; Embodiment 2 and embodiment 3 meet the requirements substantially, but performance is general; Embodiment 4 function admirables are proper electrode pairing schemes.
According to data in the table 2, with
Right
Mapping is near linear as shown in Figure 6, obtains the slope of straight line by match, and this value is reaction activity Ea.According to shown in Figure 6, embodiment 5 cell activation can be 58.18, and embodiment 6 cell activation can be 36.10.By the comparison standard scale as can be seen, embodiment 5 batteries are defective, and embodiment 6 batteries are qualified, and the technology of pole piece F is more reasonable.
Characteristics of the present invention are to use specifies mould to prepare simulated battery or half-cell, the reaction activity when different pole pieces make up in the specified for temperature ranges is calculated in Arrhenius empirical equation (Arrhenius) test after utilization is simplified, size according to reaction activity, set up the standard of judging the electrode matching degree, the pole piece performance that effectively evaluating is relevant.The method is applicable to the prepared pole piece of various lithium ion battery plus-negative plate materials, can apply to technology assessment widely, raw material assessment etc.Flow process is simple to operation, and data quick and precisely effectively reduce Material Cost and time cost in the related work.Battery mould provided by the present invention, its assembling is simple and easy, and the accuracy height can reuse.
The present invention utilizes the above-mentioned characteristic of activation energy, the computing formula (Arrhenius empirical equation) of activation energy is fit to the correction of electrochemical system, the method of a kind of quick evaluation both positive and negative polarity pole piece matching degree and pole piece technology is provided, has effectively avoided the waste of manpower and materials.
The present invention uses and specifies mould to prepare simulated battery, the reaction activity when different pole pieces make up in the specified for temperature ranges is calculated in Arrhenius empirical equation (Arrhenius) test after utilization is simplified, can set up the standard of judging battery performance, the matching degree of effectively evaluating battery pole piece.
The present invention is when being used to estimate pole piece preparation technology, and the research electrode is for specifying the negative or positive electrode sheet, is that the half-cell of metal lithium sheet carries out aforesaid operations to electrode.
The method of quick evaluation battery positive/negative plate matching degree provided by the invention, raw material and pole piece performance is simple to operate, and data are accurate, simultaneously a large amount of savings material, time, human cost, compared to common method in the industry remarkable advantages is arranged.For auxiliary pole piece, battery design great Practical significance is arranged.
Claims (10)
1. battery mould, it is characterized in that, the middle part that comprises tubular, with the end that is arranged on two ends, described tubular middle part, described end is provided with the lug boss that cooperates with this through hole corresponding to the position of described middle part axially extending bore, and after the assembling, described lug boss is clipped in the simulated battery in the mould in the through hole at described middle part, described end is provided with the lug that connects of drawing lead, and described two ends are the conducting by mould self not.
2. battery mould according to claim 1, it is characterized in that described lug boss is provided with external screw thread, described through hole is provided with corresponding internal thread, described lug boss and described through hole make described end be connected with described middle part by rotation by threads engaged.
3. battery mould according to claim 1 is characterized in that, silica gel sealing ring and polytetrafluoroethylene film sealing are used in the junction of described middle part and end.
4. battery mould according to claim 1 is characterized in that described lug boss is provided with spring, and described spring closely contacts the positive/negative plate of simulated battery.
5. battery mould according to claim 1 is characterized in that, the material of described end is one or more of iron, copper, aluminium and metal thereof, non-metal alloy, and the material at described middle part is polytetrafluoroethylene, nylon, polymethyl methacrylate or PP.
6. method of estimating fast the battery matching degree, it is characterized in that, use and prepare simulated battery as any described mould among the claim 1-5, utilize AC impedence method to measure electrochemical reaction resistance R ct under the simulated battery different temperatures of various combination by the lead-in wire that connects lug, calculate reaction activity by the Arrhenius empirical equation, determine the degree of different batteries couplings by comparison activation energy value: when activation energy numerical value is low more, the battery matching degree is good more; When activation energy numerical value is high more, the battery matching degree is poor more.
7. the method for quick evaluation battery matching degree according to claim 6 is characterized in that described AC impedence method comprises the steps:
Simulated battery is carried out charge and discharge cycles 3 times, and multiplying power is 0.2C, is used for activation;
Simulated battery after the activation is carried out the test of electrochemical AC impedance spectrum, amplitude is 1 to 50mV, high frequency frequency 1KHz to 1MHz, low frequency frequency 0.00001Hz to 10Hz, test is appointed in-20 ℃ to 100 ℃ temperature ranges and is got 3 to 100 temperature spots and carry out repetition, obtains electrochemical reaction resistance R ct by The Fitting Calculation;
Utilize the Arrhenius empirical equation after simplifying
, with
Right
Mapping is tried to achieve reaction activity by slope, and wherein, Ea is an activation energy, and T is a temperature, and A is a pre-exponential factor.
8. the method for quick evaluation battery matching degree according to claim 6, it is characterized in that, the positive pole of described simulated battery comprises one or more in LiFePO4, cobalt acid lithium, LiMn2O4, nickel cobalt manganese, the nickel cobalt aluminium commercialization lithium ion secondary battery anode material, and negative pole comprises one or more in native graphite, Delanium, silicon, the metal oxide negative material.
9. the method for quick evaluation battery matching degree according to claim 6 is characterized in that, described simulated battery is the half-cell of metal lithium sheet for specifying the negative or positive electrode sheet to electrode.
10. the method for quick evaluation battery matching degree according to claim 6 is characterized in that, when activation energy was less than or equal to 30, the battery matching degree was good; When activation energy greater than 30 less than 40 the time, the battery matching degree is qualified; When activation energy more than or equal to 40 the time, the battery matching degree is defective.
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| CN102901533A (en) * | 2012-11-05 | 2013-01-30 | 辽宁弘光科技(集团)有限公司 | Die for detecting stimulated battery |
| CN103389465A (en) * | 2012-05-11 | 2013-11-13 | 光阳工业股份有限公司 | Method for measuring electric quantity of battery |
| CN104868180A (en) * | 2014-09-30 | 2015-08-26 | 北汽福田汽车股份有限公司 | Grouping method and grouping system of single batteries |
| CN105006597A (en) * | 2015-05-18 | 2015-10-28 | 北京波士顿动力电池有限公司 | Method for fast evaluating conformity of lithium ion battery electrode production with symmetric electrodes |
| CN109001638A (en) * | 2018-06-22 | 2018-12-14 | 格林美（无锡）能源材料有限公司 | A kind of method of Fast Evaluation positive electrode cladding front and back DCR |
| CN110245870A (en) * | 2019-06-19 | 2019-09-17 | 河北工业大学 | A kind of method of the determining optimal matching method in vehicle-mounted relay contact |
| CN111175663A (en) * | 2020-02-17 | 2020-05-19 | 李树成 | Method and instrument for testing activation internal resistance of battery |
| CN111781253A (en) * | 2020-06-19 | 2020-10-16 | 国联汽车动力电池研究院有限责任公司 | Device and method for measuring desolvation activation energy of lithium ions in electrolyte |
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| CN104868180A (en) * | 2014-09-30 | 2015-08-26 | 北汽福田汽车股份有限公司 | Grouping method and grouping system of single batteries |
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| CN109001638A (en) * | 2018-06-22 | 2018-12-14 | 格林美（无锡）能源材料有限公司 | A kind of method of Fast Evaluation positive electrode cladding front and back DCR |
| CN110245870A (en) * | 2019-06-19 | 2019-09-17 | 河北工业大学 | A kind of method of the determining optimal matching method in vehicle-mounted relay contact |
| CN111175663A (en) * | 2020-02-17 | 2020-05-19 | 李树成 | Method and instrument for testing activation internal resistance of battery |
| CN111781253A (en) * | 2020-06-19 | 2020-10-16 | 国联汽车动力电池研究院有限责任公司 | Device and method for measuring desolvation activation energy of lithium ions in electrolyte |
| CN111781253B (en) * | 2020-06-19 | 2023-04-07 | 国联汽车动力电池研究院有限责任公司 | Device and method for measuring desolvation activation energy of lithium ions in electrolyte |
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Address after: 201203 Shanghai City, Pudong New Area China Zuchongzhi Road (Shanghai) Free Trade Zone No. 73 Lane 887 Patentee after: Shanghai ZTE energy Polytron Technologies Inc Address before: 201203 Shanghai city Pudong New Area Zuchongzhi Road No. 73 Lane 887 Patentee before: Zhongxing (Shanghai) Pylon Technology Co., Ltd. |
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| CP01 | Change in the name or title of a patent holder |
Address after: 201203 Pudong New Area, Shanghai, China (Shanghai) free trade trial area, 887 Lane 73, Chong Chong Road. Patentee after: Shanghai PON energy Polytron Technologies Inc Address before: 201203 Pudong New Area, Shanghai, China (Shanghai) free trade trial area, 887 Lane 73, Chong Chong Road. Patentee before: Shanghai ZTE energy Polytron Technologies Inc |
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