CN101645521A - Low temperature functional electrolyte of lithium-ion secondary battery and preparation method thereof - Google Patents
Low temperature functional electrolyte of lithium-ion secondary battery and preparation method thereof Download PDFInfo
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- CN101645521A CN101645521A CN200910095545A CN200910095545A CN101645521A CN 101645521 A CN101645521 A CN 101645521A CN 200910095545 A CN200910095545 A CN 200910095545A CN 200910095545 A CN200910095545 A CN 200910095545A CN 101645521 A CN101645521 A CN 101645521A
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Abstract
The invention mainly relates to a method for preparing low temperature functional electrolyte of a lithium titanate (Li4Ti5O12) lithium-ion secondary battery. The functional electrolyte has the advantage that the electrolyte is suitable for high multiplying power exertion of lithium titanate material at the low temperature (-20 DEG C), thus having extreme property. The method comprises: compounding commercial electrolyte lithium salt LiPF6 and lithium salts (such as LiBF4, LiN(SO2CF3) 2 and LiODFB) with excellent low temperature property, and optimizing an electrolyte low temperature system byreducing or abandoning film-forming solvent EC with poor low temperature property and increasing low boiling point solvents such as PC, EA, THF and the like with the excellent low temperature property aiming at the characteristic of no SEI film of the Li4Ti5O12 battery. Meanwhile, a small quantity of additive is added to stabilize the interface stability of the lithium salts.
Description
Technical field
The present invention relates to the lithium-ion battery electrolytes system, specifically a kind ofly be used for the low temperature functional electrolyte and preparation method thereof that negative material is the lithium rechargeable battery of lithium titanate.
Background technology
In recent years, because the pressure of environmental pollution and energy shortage forces various countries to strive to find the energy of new green, environmental protection, sustainable development.The green high-capacity environment-protecting lithium ion battery that occurs the nineties in 20th century because its energy density height, have extended cycle life, the operating voltage advantages of higher, make it become one of electrical source of power that attracts most attention.Spinel type lithium titanate (Li
4Ti
5O
12) be a kind of unstressed insertion material, recurring structure does not change in charge and discharge process, good cycle, good charge and discharge platform, specific capacity height are arranged and concentrate on land regions with electrolyte reaction, low price, preparation easily simultaneously.Compare with commercial carbon negative pole material, have better chemical property and fail safe usually, compare with the alloy type negative material, easier preparation, cost is lower.Therefore, regarded as one of novel negative material of the most promising lithium ion battery by people.
Lithium-ion battery electrolytes is being born the effect of transmission ion between the both positive and negative polarity as one of core material of battery in the inside of battery, it has significant effects to the characteristics such as capacity, operating temperature range, cycle performance and security performance of battery.The lithium salts LiPF that uses always in the present business-like lithium ion battery
6The low-temperature conductivity of base electrolyte is lower, and usually and ethylene carbonate (EC) share and be made into electrolyte and could form effective SEI film at negative pole, but the fusing point of EC higher (37 ℃), this has limited the low temperature serviceability of battery.LiN (SO
2CF
3)
2, novel lithium salts such as LiODFB is owing to have lower charge-transfer resistance, compares LiPF
6More superior cryogenic property, but its electrical conductivity at room temperature is on the low side relatively again.Have inevitable shortcoming at single lithium salts, compound lithium salts is because its common advantage that combines multiple lithium salts has been subjected to comprising the extensive concern of scientific research institutions such as AUS laboratory, Arogonne National Laboratory.
At present both at home and abroad to Li
4Ti
5O
12The research emphasis of secondary cell concentrate on material modification and with the collocation of positive electrode on, and the research of its matched electrolytic solution is rarely had report.So far Li
4Ti
5O
12On the disclosed patent of secondary cell, Sony Corp (WO99/04442) is not described electrolyte in the patent of lithium titanate battery in detail; And other reports general direct employing LiPF
6Salt is dissolved in the higher conventional organic solvent of EC content, is configured to electrolyte.As: Sanyo Electric Co., Ltd (publication number CN1841820A) directly adopts 1M LiPF
6/ EC-DEC (1: 2, volume ratio) electrolyte is as the lithium titanate battery electrolyte; Toshiba Corporation (publication number CN 1862870A) lithium titanate battery adopts LiPF
6Be dissolved in the electrolyte that the EC based solvent is formed; Tianjin Bamo Technology Co (publication number CN101262078A) then adopts single LiPF
6Be dissolved in the multicomponent mixture solvent that contains EC for electrolytic salt and be configured to the lithium titanate battery electrolyte.
Above-mentioned electrolyte adopts the film forming solvent EC of high-load on the one hand, because the EC fusing point is higher, causes the lithium salts crystallization to be separated out at low temperatures easily and causes the poorness of electrolyte lithium ion; On the other hand owing to adopted the LiPF of poor performance at low temperatures
6As single electric conducting lithium salt, seriously undermined the conductivity and the diffusion coefficient of electrolyte equally, these two factors have greatly influenced present Li
4Ti
5O
12The cryogenic property of secondary cell, especially low temperature multiplying power and cycle performance.
Summary of the invention
The present invention is directed to prior art Li
4Ti
5O
12The low temperature multiplying power that secondary cell electrolyte exists and the deficiency of cycle performance provide a kind of and can promote Li significantly
4Ti
5O
12The secondary cell capacity performance and the low temperature functional electrolyte of the lithium ion battery-metatitanic acid secondary lithium batteries of multiplying power property and preparation method thereof at low temperatures.
The objective of the invention is to be implemented by the following technical programs:
The low temperature functional electrolyte of lithium rechargeable battery, its component comprises compound lithium salts, organic solvent and additive; Compound lithium salts is by LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiCF
3SO
3, LiN (SO
2CF
3)
2, two kinds or two or more compositions among LiBOB, the LiODFB; Organic solvent was made up of one or more kinds of composition the in ethylene carbonate (EC), propene carbonate (PC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl acetate (EA), N-methyl pyrrolidone (NMP), oxolane (THF), the dimethyl ether organic solvents such as (DME); Additive is made up of in vinylene carbonate (VC), propane sultone (PS), cyclohexylbenzene, trimethyl phosphate, the fluoro methyl carbonic acid vinyl acetate one or more.
The low temperature functional electrolyte of above-mentioned lithium rechargeable battery, as preferably, its component concentration content by mass percentage comprises compound lithium salts 8wt%～14wt%, organic solvent 84wt%～90wt%, additive 1%～4%.
The low temperature functional electrolyte of above-mentioned lithium rechargeable battery, as preferably, the mass percent concentration content of compound lithium salts is 9%～12%.
The low temperature functional electrolyte of above-mentioned lithium rechargeable battery, as preferably, the mass percent concentration content of additive is 1%～3%.
The low temperature functional electrolyte of above-mentioned lithium rechargeable battery, as preferably, the content of PC occupies that the 30wt% of machine solvent is above, EC content occupies below the 5wt% of machine solvent in the organic solvent.
The low temperature functional electrolyte of above-mentioned lithium rechargeable battery, as preferably, require lithium salts purity greater than the purity of 99.9wt%, additive and solvent be higher than 99.9wt%, moisture is lower than 20ppm (mass ratio), metal ion is less than 20ppm (mol ratio), acidity is less than 50ppm.
The preparation method of the low temperature functional electrolyte of above-mentioned lithium rechargeable battery, its step comprises:
The first step: will mix by purifying removal of impurities, the low-temperature solvent that removes water treatment;
Second step: at ambient temperature, the composite conducting lithium salts is added in the above-mentioned solvent, stirs;
The 3rd step: in electrolyte, add certain quantity of additive, be made into certain density electrolyte;
The particular content of above-mentioned steps is as follows.
The first step: under 22 ℃～250 ℃ conditions, the organic solvent of different boiling is distilled purification, remove the minor amount of water in the organic solvent simultaneously, utilize molecular sieve organic solvent being carried out degree of depth adsorb traces water then, such operation is carried out once or once, until impurity, moisture＜0.005wt% repeatedly;
Second step: take by weighing compound lithium salts, then it is added in the above-mentioned organic solvent, stir, clarification, no post precipitation leave standstill and are not less than half an hour in solution, obtain mixed solution;
The 3rd step: take by weighing additive, slowly pour in the described mixed solution of step, stir, leave standstill, obtain low temperature functional electrolyte.
As preferably, compound lithium salts is by LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiCF
3SO
3, LiN (SO
2CF
3)
2, two kinds or two or more compositions among LiBOB, the LiODFB; Organic solvent was made up of one or more kinds of composition the in ethylene carbonate (EC), propene carbonate (PC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl acetate (EA), N-methyl pyrrolidone (NMP), oxolane (THF), the dimethyl ether organic solvents such as (DME); Additive is made up of in vinylene carbonate (VC), propane sultone (PS), cyclohexylbenzene, trimethyl phosphate, the fluoro methyl carbonic acid vinyl acetate one or more.
As preferably, all processes of the preparation of described mixed solution are all carried out in being full of the atmosphere of high-purity argon gas.
As preferably, the molecular sieve that the impurity removal process that dewaters adopts can adopt 3A, 4A or 5A.
As preferably, in the described first step, organic solvent has also comprised blend step, PC, EMC, EA is carried out ternary solvent mix, and three's mass ratio is 3: 5: 3.
As preferably, in the described first step, organic solvent has also comprised blend step, PC, EMC, THF is carried out ternary solvent mix, and three's mass ratio is 5: 3: 2.
As preferably, in the described first step, organic solvent has also comprised blend step, PC, DEC, EA is carried out ternary solvent mix, and three's mass ratio is 4: 3: 3.
As preferably, in the described first step, organic solvent has also comprised blend step, PC, EMC is carried out ternary solvent mix, and both mass ratioes are 4: 3.
In the first step, the purifying removal of impurities, remove water treatment technology and comprise one or more combination in cosolvent method, boulton process, distillation crystallisation, the molecular sieve adsorption.Can also adopt simultaneously any one the above material in active carbon, calcium hydride, lithium hydride, anhydrous calcium oxide, calcium chloride, non-oxidation two phosphorus, alkali metal or the alkaline-earth metal; The molecular sieve that the impurity removal process that dewaters adopts can adopt 3A, 4A and 5A, preferred 5A or 4A.
Described low-temperature solvent comprises any one or more than one the mixing among cyclic carbonate ester solvent such as PC, MPC, linear carbonate solvent such as DEC, EMC, other mixed solvent such as GBL, EA, EA, THF, DME, the NMP; The mass percent of used organic solvent is 84～90%, and purity should be greater than 99.95%, and metal ion and HF concentration all satisfy battery request.Content 〉=30%, the EC content of preferred PC are not higher than 5%;
Described electric conducting lithium salt is LiPF
6, LiBF
4, LiAsF
6, LiCF
3SO
3, LiN (CF
3SO
3)
2With any one or the multiple combination among the LiDFOB.Preferred LiBF
4, LiPF
6With LiBOB, LiODFB, LiN (SO
2CF
3)
2Between combination.Wherein the mass percent concentration content of compound lithium salts is preferably 9%～12% 8%～14%;
Described additive is one or more combinations that comprise in PS, VC, cyclohexylbenzene, trimethyl phosphate, the fluoro methyl carbonic acid vinyl acetate, the combination of preferred PS or VC; Wherein the mass percent concentration content of additive preferably is not higher than 3% 1%～4%;
In low temperature functional electrolyte lithium ion battery of the present invention, negative electrode active material is a lithium titanate, and positive active material comprises LiMn2O4, cobalt acid lithium, lithium nickelate and LiFePO4, more preferably selects LiMn2O4.
Material of the present invention compared with prior art has the following advantages:
1. the present invention can improve present single commercial electrolytic salt LiPF significantly by the electrolytic salt prescription is improved
6The shortcoming of dissolution in low temperature poor performance.
2. the present invention is by abandoning or the requisite film for additive EC of the present commercial electrolyte of little usefulness, and by pure low-temperature solvent, the especially optimization of ultralow temperature solvent further improves the cryogenic property of EC base electrolyte.
By the cryogenic property optimization of salt and solvent, capacity, cycle performance and the multiplying power property of lithium titanate battery under low-temperature condition is not fully exerted.
Description of drawings
Fig. 1 is embodiment 1, embodiment 2, embodiment 3, embodiment 4 electrolyte lithium titanate batteries and the contrast discharge curve (1C) of comparative example's electrolyte lithium titanate battery under-20 ℃;
Fig. 2 is the multiplying power discharging curve of embodiment 1 electrolyte lithium titanate battery under-20 ℃;
Fig. 3 is the multiplying power discharging curve of comparative example's electrolyte lithium titanate battery under-20 ℃;
Fig. 4 embodiment 1,2 electrolyte lithium titanate batteries and the contrast cyclic curve of comparative example's electrolyte lithium titanate battery under-20 ℃ of conditions.
Embodiment
Below be the specific embodiment of the present invention, technical characterictic of the present invention is described further, but the present invention is not limited to these embodiment.
Embodiment 1:
Under 25 ℃ of conditions of the first step, at first utilize Rotary Evaporators that organic solvent PC, EMC and EA are distilled purification respectively, remove the minor amount of water of the inside, utilize the 4A molecular sieve under 40 ℃ of conditions, to carry out degree of depth adsorb traces water respectively then.Such operation is carried out three times repeatedly, until impurity, moisture＜0.005%.PC, EMC, EA carry out the ternary solvent mixing subsequently, respectively take by weighing a certain amount of PC, EMC and EA with the micro-analysis electronic balance, and wherein three's mass ratio is 3: 5: 3, measures the 100ml mixed electrolytic solution with graduated cylinder (250ml) and pours port grinding bottle into.All processes of the preparation of electrolyte are all carried out in being full of the glove box of high-purity argon gas;
Second step took by weighing 10g LiPF with the micro-analysis electronic balance in glove box under 25 ℃ of conditions
6With 2g LiODFB.Then it is added on (in the port grinding bottle) in the above-mentioned ternary mixed solvent, stirs, clarification, no post precipitation left standstill 2 hours in solution;
The 3rd step took by weighing 1g VC with the micro-analysis electronic balance in glove box under 25 ℃ of conditions, slowly pour in the described electrolyte of step, stirred, and left standstill 2 hours.Pour electrolyte into the aluminum hull air-tight bottle, promptly be made into LiPF
6-LiODFB/PC-EMC-EA-VC low temperature functional electrolyte;
As mentioned above, prepare lithium titanate lithium ion battery low temperature functional electrolyte of the present invention.
Embodiment 2:
Under 25 ℃ of conditions of the first step, at first utilize Rotary Evaporators that organic solvent PC, EMC, THF are distilled purification respectively, remove the minor amount of water of the inside, utilize the 4A molecular sieve under 40 ℃ of conditions, to carry out degree of depth adsorb traces water respectively then.Such operation is carried out three times repeatedly, until impurity, moisture＜0.005%.PC, EMC, THF carry out the ternary solvent mixing subsequently, respectively take by weighing a certain amount of PC, EMC, THF with the micro-analysis electronic balance, and wherein three's mass ratio is 5: 3: 2, measures the 100ml mixed electrolytic solution with graduated cylinder (250ml) and pours port grinding bottle into.All processes of the preparation of electrolyte are all carried out in being full of the glove box of high-purity argon gas;
Second step took by weighing 8g LiPF with the micro-analysis electronic balance in glove box under 25 ℃ of conditions
6With 4g LiBF
4Then it is added on (in the port grinding bottle) in the above-mentioned ternary mixed solvent, stirs, clarification, no post precipitation left standstill 2 hours in solution;
The 3rd step took by weighing 0.5g VC and 0.5g PS with the micro-analysis electronic balance in glove box under 25 ℃ of conditions, slowly pour in the described electrolyte of step, stirred, and left standstill 2 hours.Pour electrolyte into the aluminum hull air-tight bottle, promptly be made into LiPF
6-LiBF
4/ PC-THF-EMC-VC-PS low temperature functional electrolyte;
As mentioned above, prepare lithium titanate lithium ion battery low temperature functional electrolyte of the present invention.
Embodiment 3:
Under 25 ℃ of conditions of the first step, at first utilize Rotary Evaporators that organic solvent PC, DEC, EA are distilled purification respectively, remove the minor amount of water of the inside, utilize the 4A molecular sieve under 40 ℃ of conditions, to carry out degree of depth adsorb traces water respectively then.Such operation is carried out three times repeatedly, until impurity, moisture＜0.005%.PC, DEC, EA carry out the ternary solvent mixing subsequently, respectively take by weighing a certain amount of PC, DEC, EA with the micro-analysis electronic balance, and wherein three's mass ratio is 4: 3: 3, measures the 100ml mixed electrolytic solution with graduated cylinder (250ml) and pours port grinding bottle into.All processes of the preparation of electrolyte are all carried out in being full of the glove box of high-purity argon gas;
Second step took by weighing 3g LiPF with the micro-analysis electronic balance in glove box under 25 ℃ of conditions
6With 6g LiN (SO
2CF
3)
2Then it is added on (in the port grinding bottle) in the above-mentioned ternary mixed solvent, stirs, clarification, no post precipitation left standstill 2 hours in solution;
The 3rd step took by weighing 0.8g VC with the micro-analysis electronic balance in glove box under 25 ℃ of conditions, slowly pour in the described electrolyte of step, stirred, and left standstill 2 hours.Pour electrolyte into the aluminum hull air-tight bottle, promptly be made into LiPF
6-LiN (SO
2CF
3)
2/ PC-DEC-EA-VC low temperature functional electrolyte;
As mentioned above, prepare lithium titanate lithium ion battery low temperature functional electrolyte of the present invention.
Embodiment 4:
Under 25 ℃ of conditions of the first step, at first utilize Rotary Evaporators that organic solvent PC, EMC are distilled purification respectively, remove the minor amount of water of the inside, utilize the 4A molecular sieve under 40 ℃ of conditions, to carry out degree of depth adsorb traces water respectively then.Such operation is carried out three times repeatedly, until impurity, moisture＜0.005%.PC, EMC carry out the ternary solvent mixing subsequently, respectively take by weighing a certain amount of PC and EMC with the micro-analysis electronic balance, and wherein both mass ratioes are 4: 3, measure the 100ml mixed electrolytic solution with graduated cylinder (250ml) and pour port grinding bottle into.All processes of the preparation of electrolyte are all carried out in being full of the glove box of high-purity argon gas.
Second step took by weighing 6g LiBF with the micro-analysis electronic balance in glove box under 25 ℃ of conditions
4With 5g LiODFB.Then it is added on (in the port grinding bottle) in the above-mentioned mixed solvent, stirs, clarification, no post precipitation left standstill 2 hours in solution; Promptly be made into LiBF
4-LiODFB/PC-EMC low temperature functional electrolyte.
As mentioned above, prepare lithium titanate lithium ion battery low temperature functional electrolyte of the present invention.
The comparative example 1: electrolyte discharge performance test under the different low temperature
Experiment contrast electrolyte is commercial electrolyte standard recipe, and promptly the prescription that provides of lithium-ion electrolyte producer is the electrolyte of 1M LiPF6/EC-DMC-EMC (1: 1: 3).
The test battery Capacity design is 20Ah (liquid flexible packing), and positive active material adopts battery division department of Wanxiang Electric Vehicle Co., Ltd. to produce used lithium manganate material (Li
2MnO
4), negative electrode active material adopts lithium titanate (Li
4Ti
5O
12) (Shenzhen Bei Terui), barrier film adopts the single-layer septum of U.S. Celgard company.
The electricity core has been made afterwards in the glove box that is full of high-purity Ar gas and have been had embodiment 1,2,3,4 and comparative example altogether five groups of electrolyte and inject electric core respectively, assembles battery.Leave standstill, change into, shelve ageing after the taking-up respectively, bleed, encapsulation, capacity demarcate.Carry out constant current charge and discharge experiment with new prestige series battery test macro at-20 ℃ then, charging current is 10A (0.5C), and discharging current is 20A (1C), and end of charge voltage is 3.0V, and final discharging voltage is 1.5V.
The comparative example 2: the test of low temperature (20 ℃) high rate performance
The lithium titanate battery is made as described in the comparative example 1 during experiment.Under normal temperature (25 ℃), embodiment 3 and contrast electrolyte battery are full of electric charge (1C charging, cut-ff voltage 3V), then test battery are discharged by 1C, 5C, 7C multiplying power after-20 ℃ high low temperature experimental box leaves standstill 12 hours.
The comparative example 3: the test of low temperature (20 ℃) cycle performance
The lithium titanate battery is made as described in the comparative example 1 during experiment.After under the low temperature (20 ℃) embodiment 1,2 electrolyte batteries and contrast electrolyte battery being put into high low temperature experimental box to leave standstill 2 hours by 0.5C charging, the test of 1C discharge carrying out cycle performance.
Specific embodiment described in the present invention only is that the present invention's spirit is illustrated.The technical staff of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment.
Although the present invention has been made detailed explanation and has quoted some instantiations as proof, to those skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (11)
1. the low temperature functional electrolyte of a lithium rechargeable battery, its component comprises compound lithium salts, organic solvent and additive; Compound lithium salts is by LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiCF
3SO
3, LiN (SO
2CF
3)
2, two kinds or two or more compositions among LiBOB, the LiODFB; Organic solvent was made up of one or more kinds of composition the in the organic solvents such as ethylene carbonate, propene carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, diethyl carbonate, dimethyl carbonate, ethyl acetate, N-methyl pyrrolidone, oxolane, dimethyl ether; Additive is made up of in vinylene carbonate, propane sultone, cyclohexylbenzene, trimethyl phosphate, the fluoro methyl carbonic acid vinyl acetate one or more.
2. the low temperature functional electrolyte of lithium rechargeable battery according to claim 1 is characterized in that, its component concentration content by mass percentage comprises compound lithium salts 8wt%～14wt%, organic solvent 84wt%～90wt%, additive 1%～4%.
3. the low temperature functional electrolyte of lithium rechargeable battery according to claim 2 is characterized in that, the mass percent concentration content of compound lithium salts is 9%～12%.
4. the low temperature functional electrolyte of lithium rechargeable battery according to claim 2 is characterized in that, the mass percent concentration content of additive is 1%～3%.
5. the low temperature functional electrolyte of lithium rechargeable battery according to claim 1 and 2 is characterized in that, the content of propene carbonate occupies that the 30wt% of machine solvent is above, ethylene carbonate content occupies below the 5wt% of machine solvent in the organic solvent.
6. the low temperature functional electrolyte of lithium rechargeable battery according to claim 1 and 2, it is characterized in that, require lithium salts purity greater than the purity of 99.9wt%, additive and solvent be higher than 99.9wt%, moisture is lower than 20ppm, metal ion is less than 20ppm, acidity is less than 50
7. the preparation method of the low temperature functional electrolyte of a lithium rechargeable battery, its step comprise,
The first step: organic solvent is distilled purification, remove the minor amount of water in the organic solvent, utilize molecular sieve organic solvent being carried out degree of depth adsorb traces water then, such operation is carried out at least once repeatedly, until impurity, moisture＜0.005wt%;
Second step: take by weighing compound lithium salts, then it is added in the above-mentioned organic solvent, stir, clarification, no post precipitation leave standstill in solution, obtain mixed solution;
The 3rd step: take by weighing additive, slowly pour in the described mixed solution of step, stir, leave standstill, obtain low temperature functional electrolyte.
8. the preparation method of the low temperature functional electrolyte of lithium rechargeable battery according to claim 7 is characterized in that, compound lithium salts is by LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiCF
3SO
3, LiN (SO
2CF
3)
2, two kinds or two or more compositions among LiBOB, the LiODFB; Organic solvent was made up of one or more kinds of composition the in the organic solvents such as ethylene carbonate, propene carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, diethyl carbonate, dimethyl carbonate, ethyl acetate, N-methyl pyrrolidone, oxolane, dimethyl ether; Additive is made up of in vinylene carbonate, propane sultone, cyclohexylbenzene, trimethyl phosphate, the fluoro methyl carbonic acid vinyl acetate one or more.
9. the preparation method of the low temperature functional electrolyte of lithium rechargeable battery according to claim 7 is characterized in that, all processes of the preparation of described mixed solution are all carried out in being full of the atmosphere of high-purity argon gas.
10. the preparation method of the low temperature functional electrolyte of lithium rechargeable battery according to claim 7 is characterized in that, the molecular sieve that the impurity removal process that dewaters adopts adopts 3A or 4A or 5A.
11. preparation method according to the low temperature functional electrolyte of claim 7 or 8 described lithium rechargeable batteries, it is characterized in that, in the described first step, organic solvent has also comprised blend step, blend step is: propene carbonate, methyl ethyl carbonate, ethyl acetate are carried out ternary solvent mix, three's mass ratio is 3: 5: 3; Or propene carbonate, methyl ethyl carbonate, oxolane are carried out ternary solvent mix, three's mass ratio is 5: 3: 2; Or propene carbonate, diethyl carbonate, ethyl acetate are carried out ternary solvent mix, three's mass ratio is 4: 3: 3; Or propene carbonate, methyl ethyl carbonate are carried out ternary solvent mix, both mass ratioes are 4: 3.
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| CN113097645A (en) * | 2021-04-02 | 2021-07-09 | 湖南立方新能源科技有限责任公司 | Composite polymer electrolyte diaphragm, preparation method thereof and solid-state battery |
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