CN102931436A - Mass triangle model-based electrolyte component optimization method - Google Patents
Mass triangle model-based electrolyte component optimization method Download PDFInfo
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- CN102931436A CN102931436A CN2012103787344A CN201210378734A CN102931436A CN 102931436 A CN102931436 A CN 102931436A CN 2012103787344 A CN2012103787344 A CN 2012103787344A CN 201210378734 A CN201210378734 A CN 201210378734A CN 102931436 A CN102931436 A CN 102931436A
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a mass triangle model-based electrolyte component optimization method, and belongs to the technical field of secondary battery reseparation. A mass triangle model is introduced into the prediction calculation of electric conductivity of electrolyte of a lithium ion battery, electric conductivity at a certain basic point is measured by an experiment, electric conductivity values at other points are predicted according to the electric conductivity of the basic point, and an electric conductivity contour line is drawn. The variation trend of the contour line is analyzed to obtain optimized electrolyte components to fulfill the aim of optimizing the electrolyte components, and improvement in the performance of the battery is experimented. Parameters are predicted accurately, a program is easy to operate, time and funds are saved, and by the optimized electrolyte, the charging and discharging performance of the battery can be improved.
Description
Technical field
The present invention relates to a kind of electrolyte component optimization method based on the quality triangle model, belong to again sorting technology field of secondary cell.
Background technology
Nowadays lithium ion battery is used widely, and expands to electric motor car, space flight, the fields such as submarine from mobile phone, notebook.Electrolyte is the important component part of lithium ion battery, mainly by lithium salts and solvent composition.Electrolyte is being born the effect of transmitting electric charge between the inside battery both positive and negative polarity, need ionic conductivity high, stable chemical nature, and Heat stability is good, safety non-pollution, cheap etc.Wherein, conductivity is one of main parameter of weighing electrolyte.High conductivity can guarantee the fast transport of lithium ion.
Electrolyte solvent is mainly used to dissolve lithium salts, and it has material impact to the first cycle efficieny of the conductivity of electrolyte, battery, reversible capacity, fail safe etc.Many performance parameters of solvent and lithium ion battery good and bad closely related, excellent solvent need that viscosity is little, fusing point is low, dielectric constant is high, redox-stable etc.It is the carbonates solvent that the electrolyte solvent of lithium ion battery adopted more, wherein, ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) etc. are the organic solvents of present several extensive uses.
EC dielectric constant large (89.78) is mainly used in dissolving lithium salts, and is the key reaction solvent of electrode surface film forming.But its fusing point is high, is unsuitable for cryogenic applications.PC fusing point low (48.8 ℃) causes material damage but easily embed altogether graphite cathode material with lithium ion.Little (the 0.65mPa s of EMC viscosity
-1), fusing point low (55 ℃), but dielectric constant little (2.958).Based on the advantages and disadvantages of single solvent physicochemical property, use mixed solvent, realizing maximizes favourable factors and minimizes unfavourable ones is to optimize electrolyte to form, realize electrode/electrolyte compatibility, the important channel of improving the electrode charge and discharge behavior.Contradiction between these parameters finally can reach optimum state by the adjusting to each solvent ratios.
The quality triangle model is widely used in metallurgy industry, is a kind of model of predicting the zone of ignorance related parameter values by given data.It is in interfacial tension, viscosity, and the function of Accurate Prediction can be brought into play in the aspects such as conductivity.
Summary of the invention
The objective of the invention is in order to solve the lithium-ion battery electrolytes multi-solvents ratio optimization problem that expends reagent and poor effect consuming time, a kind of method that the solvent component is optimized based on the quality triangle model has been proposed, by the quality triangle model Free Region is predicted, after obtaining predicting the outcome by analyzing the data electrolyte that is optimized.
The objective of the invention is to be achieved through the following technical solutions.
A kind of electrolyte component optimization method based on the quality triangle model of the present invention, the quality triangle model is introduced in the prediction and calculation of lithium-ion battery electrolytes conductivity, by the conductivity of some basic point of measuring, dope the conductivity value of other points and draw the conductivity contour according to the conductivity of basic point.Form by the electrolyte that the contour analysis of trend is optimized, reach the purpose that the electrolyte component is optimized, the raising of final experimental cell performance; Concrete steps are as follows:
1) parameter of selecting required solvent species and will surveying according to the battery applications needs is variable if solvent species, is drafted first certain mass ratio of three kinds greater than three kinds, and other are quantitative;
2) according to the physical and chemical parameter characteristics of every kind of solvent, demarcate every kind of operable upper and lower bound of solvent;
3) fasten the upper and lower bound that draws these three kinds of solvents at trigonometric coordinates, surround a Free Region by six lines; The upper and lower bound of solvent refers to guarantee battery operated normal boundary;
4) choose 5～20 points in the boundary line of Free Region as basic point, as the basis of afterwards model calculating; Recorded the conductivity value of these basic points by experiment;
5) with the conductivity value input quality triangle model calculation procedure of these basic points, gone out the conductivity value of each point in the Free Region by computer calculation, and draw out the conductivity value contour;
6) follow according to the isocontour variation tendency of conductivity value, seek and for the peaked composition point of conductivity, to be called the conjecture point at the white space that predicts the outcome or the complicated zone of conductivity value variation.By the conductivity value of measuring conjecture point, if greater than the conductivity value of all basic points, namely obtain the optimized proportion value of these three kinds of solvents; Otherwise the maximum that calculates by quality triangle model calculation procedure is the final optimization pass result.
7) three kinds of solvents of optimized proportion are considered as a variable, repeating step 2) to 6) further other solvents of not optimizing are optimized, finally obtain the optimized proportion value of all solvents;
8) the final resulting optimization electrolyte of configuration in the argon gas glove box, assembled battery test correlated performance.
Above-mentioned steps 1) solvent in is a kind of or its mixture in carbonic ester, carboxylate, the ether solvent;
Above-mentioned steps 1) battery applications comprises the application of optimizing high temperature, cryogenic property or electrochemical window in;
Above-mentioned steps 1) parameter of optimizing can be electrolytic conductivity or viscosity;
Above-mentioned steps 4) to count be 7～10 on the basis in;
Above-mentioned steps 8) assembled battery can be LiFePO in
4, LiCoO
2Or the battery of the various battery materials assemblings such as ternary material.
Beneficial effect
Parameter prediction is accurate among the present invention, and program easily operates, and saves time and economizes on the use of funds.Electrolyte after the optimization can improve the charge-discharge performance of battery.
Description of drawings
Fig. 1 is Free Region and basic point distribution map;
Fig. 2 is that normal temperature predicts the outcome;
Fig. 3 is-40 ℃ predicting the outcome;
Fig. 4 is the white space bounds;
Fig. 5 is that white space predicts the outcome;
Fig. 6 is LiCoO
2/ Li battery discharge curve chart (0.2C).
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is elaborated.
Embodiment
A kind of method based on quality triangle model prediction electrolytic conductivity, concrete operation step is as follows:
1) for satisfying cryogenic applications, selecting ethylene carbonate (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) is low-temperature solvent, optimizes electrolyte component with the quality triangle model and improves conductivity;
2) determine the solvent usable range, take the quality of three of EC, PC, EMC with as 1 part of calculating, wherein EC accounts for 0.1～0.4 part, and PC accounts for 0.1～0.6 part, and EMC accounts for 0.1～0.7 part;
3) selecting the point in the table 1 is basic point, and table 1 is the basic point coordinate; The Free Region that these basic points surround in trigonometric coordinates system as shown in Figure 1;
Table 1 basic point coordinate
4) configuration 1#～7# electrolyte, test normal temperature and-40 ℃ of conductivity.
5) with test result input quality triangle model calculation procedure, obtain Output rusults, as shown in Figures 2 and 3;
6) as shown in Figure 3, Free Region lower left corner part is white space, white space is used the prediction of quality triangle model calculation procedure and is predicted the outcome, as shown in Figure 4 and Figure 5; According to the result, selected F point is conjecture point configuration electrolyte; The conductivity value that mensuration F is ordered is 0.745mS/cm, and as shown in Figure 5, F point conductivity is the maximum of all available points;
7) electrolyte that configuration F is ordered in the argon gas glove box is assembled LiCoO with the electrolyte that F is ordered
2/ Li battery, normal temperature circulated for three weeks, and (2.8V～4.5V) is placed on the discharge performance of-40 ℃ of tests, 0.2C in the cryogenic box to the Charging state of 4.5V, cut-ff voltage is 2.5V, as shown in Figure 6.
Test result; Predicting the outcome among Fig. 3 shows that the Free Region lower left corner is that conductivity upper zone and conductivity contour are sparse not zoning of blank arranged; After dwindling research range, further predict the outcome as shown in Figure 5, not zoning of blank is still arranged among the figure.The F point of selected white space is the research point, finds after electrolyte is measured conductivity through configuring, and the conductivity that F is ordered is 0.745mS cm
-1, improved 51.4% (0.492mS cm than the B point of not optimizing
-1); Do-40 ℃ of discharge tests and show through the assembling button cell: the electrolyte that the used for electrolyte after the optimization is better than not optimizing in the performance of lithium ion battery low temperature discharge.
Claims (6)
1. electrolyte component optimization method based on the quality triangle model is characterized in that step is as follows:
1) parameter of selecting required solvent species and will surveying according to the battery applications needs is variable if solvent species, is drafted first certain mass ratio of three kinds greater than three kinds, and other are quantitative;
2) according to the physical and chemical parameter characteristics of every kind of solvent, demarcate every kind of operable upper and lower bound of solvent;
3) fasten the upper and lower bound that draws these three kinds of solvents at trigonometric coordinates, surround a Free Region by six lines; The upper and lower bound of solvent refers to guarantee battery operated normal boundary;
4) choose 5～20 points in the boundary line of Free Region as basic point, as the basis of afterwards model calculating; Recorded the conductivity value of these basic points by experiment;
5) with the conductivity value input quality triangle model calculation procedure of these basic points, gone out the conductivity value of each point in the Free Region by computer calculation, and draw out the conductivity value contour;
6) follow according to the isocontour variation tendency of conductivity value, seek and for the peaked composition point of conductivity, to be called the conjecture point at the white space that predicts the outcome or the complicated zone of conductivity value variation; By the conductivity value of measuring conjecture point, if greater than the conductivity value of all basic points, namely obtain the optimized proportion value of these three kinds of solvents; Otherwise the maximum that calculates by quality triangle model calculation procedure is the final optimization pass result;
7) three kinds of solvents of optimized proportion are considered as a variable, repeating step 2) to 6) further other solvents of not optimizing are optimized, finally obtain the optimized proportion value of all solvents;
8) the final resulting optimization electrolyte of configuration in the argon gas glove box, assembled battery test correlated performance.
2. a kind of electrolyte component optimization method based on the quality triangle model according to claim 1 is characterized in that: step 1) in solvent be a kind of or its mixture in carbonic ester, carboxylate, the ether solvent.
3. a kind of electrolyte component optimization method based on the quality triangle model according to claim 1 is characterized in that: step 1) in battery applications comprise the application of optimizing high temperature, cryogenic property or electrochemical window.
4. a kind of electrolyte component optimization method based on the quality triangle model according to claim 1 is characterized in that: step 1) parameter optimized can be electrolytic conductivity or viscosity.
5. a kind of electrolyte component optimization method based on the quality triangle model according to claim 1 is characterized in that: step 4) in to count be 7～10 on the basis.
6. a kind of electrolyte component optimization method based on the quality triangle model according to claim 1 is characterized in that: step 8) in assembled battery can be LiFePO
4, LiCoO
2Or ternary material battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023103150A1 (en) * | 2021-12-08 | 2023-06-15 | 清华大学 | Design method, apparatus and device for electrolyte, and medium and program product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023103150A1 (en) * | 2021-12-08 | 2023-06-15 | 清华大学 | Design method, apparatus and device for electrolyte, and medium and program product |
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Application publication date: 20130213 |