CN101867064A - Low temperature type lithium ion battery electrolyte with high temperature property and lithium ion battery - Google Patents
Low temperature type lithium ion battery electrolyte with high temperature property and lithium ion battery Download PDFInfo
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- CN101867064A CN101867064A CN201010199813A CN201010199813A CN101867064A CN 101867064 A CN101867064 A CN 101867064A CN 201010199813 A CN201010199813 A CN 201010199813A CN 201010199813 A CN201010199813 A CN 201010199813A CN 101867064 A CN101867064 A CN 101867064A
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Abstract
The invention discloses a low temperature type lithium ion battery electrolyte with high temperature property and lithium ion battery. The electrolyte is made by uniformly mixing and confecting electrolytic salt, non-water organic solvent, alkali additive and film-forming additive, the electrolytic salt is mixed lithium salt made by uniformly mixing lithium tetrafluoroborate and lithium bis(oxalate)borate, and the mol ratio of the two is 96-73: 4-27, the concentration of the mixed lithium salt solution formed by the electrolytic salt and the non-water organic solvent is 0.8-1.2mol/L; the alkali additive is heptamethyldisilazane and the mass ratio of the hepatmethyldisilazane and the non-water organic solvent is 0.1-8%; the mass ratio of the film-forming additive and the non-water organic solvent is 0.1-5%; and the lithium ion battery comprises an anode, a cathode, a diaphragm and low temperature type lithium ion battery electrolyte with high temperature property. The invention has reasonable design, simple preparation method steps and convenient implementation, and the prepared electrolyte and lithium ion battery have favourable comprehensive performances.
Description
Technical field
The present invention relates to a kind of lithium-ion battery electrolytes and use the lithium ion battery of this electrolyte, especially relate to a kind of electrolyte of low temp lithium ion battery and lithium ion battery of taking into account high-temperature behavior.
Background technology
Energy crisis, shortage of resources and environmental pollution are the severe challenges that human survival faces, and seek secondary energy sources clean, renewable, resource-conserving and be one of task that human social needs to be resolved hurrily.Lithium ion battery is the new generation of green environment-friendly battery that the eighties of last century the nineties grows up, its have voltage height, specific energy big, discharge and recharge characteristics such as life-span length, safety, environmental protection, become dominating of compact power and electrical source of power.Along with the lithium ion battery marketization deepens continuously, people are more and more higher to the expectation of battery performance, and the lithium-ion electric pool technology is just towards military domain and aerospace field development.And that all compare the performance requirement of lithium ion battery in these fields is harsh, be mainly reflected in high temperature performance, cycle performance and the fail safe, and electrolyte to form be one of key factor of these performances of decision.
At present, the commercialization lithium ion battery adopts native graphite, carbonaceous mesophase spherules material with carbon elements such as (MCMB) negative pole as battery mostly, with LiCo0
2, LiMn
2O
4, LiNiO
2Deng embed and the material of removal lithium embedded as the positive pole of battery, with the non-aqueous organic solvent that is dissolved with lithium salts electrolyte as lithium ion battery.Nowadays, Shang Yong electrolytic salt great majority are lithium hexafluoro phosphate (LiPF
6), but its shortcoming is extremely responsive to moisture, and lack temperature stability, thereby restricted its high temperature performance greatly.Studies show that in a large number: LiBF4 (LiBF
4Though) conductivity do not have LiPF in the same solvent
6The conductivity height, but LiBF
4Base electrolyte has good low temperature performance, and polarization is very little down at-30 ℃.And biethyl diacid lithium borate (LiBOB) is a kind of novel lithium salts of developing in recent years, and its distinctive thermal stability and high temperature film forming are considered to the most potential replacement LiPF
6Novel electrolytes salt.For the advantage of comprehensive various lithium salts, Many researchers adopts two kinds of compound or a kind of lithium salts of salt to improve the cryogenic property of electrolyte as the form of additive.Organic solvent commonly used has ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Methylethyl carbonic ester (EMC), methyl acetate (MA), ethyl acetate (EA), methyl formate (MF) etc., by optimizing the proportioning of solvent composition and relative quantity, reduce the content of high melting point component EC and increase the content of low viscosity, low-melting component, the low-temperature conductivity of electrolyte can be effectively improved, thereby the purpose of improving the lithium ion battery cryogenic property can be reached.
At present, the conventional lithium-ion battery electrolytes that uses only is about 80%-20 ℃ of following discharge capacities, and-40 ℃ can not put electric weight substantially, and the most of low-temperature electrolytes in the industry also only have low temperature performance, its cycle performance and high-temperature behavior are all relatively poor, thereby have limited the range of application of lithium ion battery widely.Therefore, how to improve the discharge performance of lithium ion battery in wide temperature range, be the direction of lithium ion battery area research worker ongoing effort always.
Summary of the invention
Technical problem to be solved by this invention is at above-mentioned deficiency of the prior art, provides that a kind of processing and preparing is easy, cost is low and high temperature performance and all good electrolyte of low temp lithium ion battery of taking into account high-temperature behavior of electrical property.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of electrolyte of low temp lithium ion battery of taking into account high-temperature behavior, by electrolytic salt, non-aqueous organic solvent, the even mixed preparing of alkalinity additive and film for additive forms, it is characterized in that: the mixing lithium salts of described electrolytic salt for evenly mixing by LiBF4 and biethyl diacid lithium borate, and the mol ratio of LiBF4 and biethyl diacid lithium borate is 96～73: 4～27, and described electrolytic salt and the described non-aqueous organic solvent concentration of mixing lithium salt solution that forms that evenly is mixed is 0.8～1.2mol/L; Described alkalinity additive is a heptamethyldisilazane, and the mass percent of described heptamethyldisilazane and described non-aqueous organic solvent is 0.1%～8%; The mass percent of described film for additive and described non-aqueous organic solvent is 0.1%～5%.
The above-mentioned electrolyte of low temp lithium ion battery of taking into account high-temperature behavior, be characterized in: described non-aqueous organic solvent is evenly mixed by conventional base solvent and low melting point solvent, and the percent by volume of described conventional base solvent and low melting point solvent is 8%～40%: 92%～60%; Described conventional base solvent is one or both in ethylene carbonate, propene carbonate, dimethyl carbonate and the diethyl carbonate, described low melting point solvent is Methylethyl carbonic ester, methyl formate, methyl acetate, ethyl acetate, methyl butyrate and 1, one or more in the 2-dimethoxy-ethane.
The above-mentioned electrolyte of low temp lithium ion battery of taking into account high-temperature behavior is characterized in: described film for additive is a vinylene carbonate, 1, one or both in 3-propane sultone and the gamma-butyrolacton.
Simultaneously, the present invention also provides a kind of high comprehensive performance and has had the low temp lithium ion battery of taking into account high-temperature behavior of good low temperature performance, low temperature high rate performance, cycle performance, high-temperature shelf property and high temperature discharge performance, comprise positive pole, negative pole and barrier film, it is characterized in that: also comprise the electrolyte of low temp lithium ion battery of taking into account high-temperature behavior.
The above-mentioned low temp lithium ion battery of taking into account high-temperature behavior is characterized in: described barrier film is the celgard2320 barrier film.
The present invention compared with prior art has the following advantages:
1, the manufacture method step of electrolyte and lithium ion battery is simple and workable, makes easily the high comprehensive performance of prepared electrolyte and lithium ion battery.The lithium ion battery of making is by transition metal lithium intercalation compound (LiCoO
2, LiMn
2O
4Or LiNiO
2Deng) as anodal, native graphite, carbonaceous mesophase spherules (MCMB) material with carbon element of etc.ing be as negative pole, the porous polyolefin compound is as barrier film, and employing lamination or winding method are made the square flexible packing lithium ion battery.
2, prepared electrolyte has excellent low temperature performance, and with traditional electrolysis liquid phase ratio, the present invention has improved the low viscous solvent composition of low melting point in the electrolyte, has widened its liquid scope greatly, more helps Li at low temperatures
+Migration, be more suitable for low temperature discharge, can under ultralow temperature (specifically being-50 ℃) condition, carry out regular picture.
3, prepared electrolyte has the good low-temperature high rate performance, general low-temperature electrolyte all discharges under the little electric current of 0.05C～0.1C, the electrolyte that the present invention makes-20 ℃ ,-30 ℃, with-40 ℃ low temperature under, all can under the situation of not overdischarge of 3V, support the 1C heavy-current discharge.
4, prepared electrolyte has higher high temperature discharge performance, general low-temperature electrolyte, only guaranteed cryogenic property, and ignored its combination property, the electrolyte that makes among the present invention has also been taken into account its high-temperature behavior under the condition that guarantees low temperature performance excellent, make and under high temperature (55 ℃, the 0.2C discharge) condition, have 97% discharge ratio.
5, prepared electrolyte has good high-temperature shelf property, owing to added alkalinity additive (specifically being heptamethyldisilazane) in the electrolyte of preparing among the present invention, make low temperature electrolytic solution inflatable not under 7 days full electricity of 60 ℃ of high temperature are stored, and have 86% capability retention and 97% capacity restoration rate, enlarged the environment for use and the range of application of this electrolyte greatly.
6, prepared electrolyte has good normal-temperature circulating performance, electrolyte matrices solvent among the present invention has adopted high-k, the good solvent EC of filming performance, and add suitable film for additive, make electrolyte among the present invention outside having good high temperature performance, do not sacrifice the electrical property of its normal temperature, have very stable normal-temperature circulating performance.
7, reasonable in design, manner of formulation is flexible and practical value is high, and popularizing application prospect is extensive, and the electrolytic salt that is adopted combines LiBF4 (LiBF
4) and the advantage of biethyl diacid lithium borate (LiBOB), and when preparation electrolyte, by optimizing solvent types, the proportioning of component and relative quantity, reduce the content of high melting point component and increase low viscosity, the content of low-melting component organic solvent, and add alkalinity additive with remarkable efficacy, effectively improved the combination property of lithium ion battery, make the lithium ion battery that finally makes have good low temperature performance, the low temperature high rate performance, cycle performance, high-temperature shelf property and high temperature discharge performance, can continuous discharge under-50～60 ℃ of temperature conditions, thereby have remarkable economical and be worth and social value.During reality preparation solvent, used conventional base solvent is one or both in ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC) or the diethyl carbonate (DEC), described low melting point solvent is Methylethyl carbonic ester (EMC), methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), methyl butyrate (MB) or 1, one or more in the 2-dimethoxy-ethane (DME).
In sum, the present invention is reasonable in design, preparation method's step simple, realize convenient and prepared electrolyte and lithium ion battery high comprehensive performance, under the prerequisite that does not influence the electrolyte cryogenic property, the high-temperature behavior and the combination property of electrolyte have been improved greatly, make electrolyte of the present invention have good high low temperature performance, low temperature high rate performance, cycle performance and high-temperature shelf property, the lithium ion battery that utilizes the present invention to make discharges under-50 ℃ of cryogenic conditions and can reach more than 50% of normal temperature discharge capacity.
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment
A kind of electrolyte of low temp lithium ion battery of taking into account high-temperature behavior disclosed in this invention is formed by the even mixed preparing of electrolytic salt, non-aqueous organic solvent, alkalinity additive and film for additive.Wherein, described electrolytic salt is by LiBF4 (LiBF
4) and the mixing lithium salts that evenly mixes of biethyl diacid lithium borate (LiBOB), and the mol ratio of LiBF4 and biethyl diacid lithium borate is 96～73: 4～27, described electrolytic salt and the described non-aqueous organic solvent concentration of mixing lithium salt solution that forms that evenly is mixed is 0.8～1.2mol/L, because when the concentration of mixing lithium salt solution too hour, the performance of made electrolyte can worsen because of the conductibility difference of lithium ion; And when the concentration of mixing lithium salt solution was too high, the animal migration of lithium ion can increase because of the viscosity of electrolyte and reduce.Described alkalinity additive is a heptamethyldisilazane, and the mass percent of described heptamethyldisilazane and described non-aqueous organic solvent is 0.1%～8%, the addition of described heptamethyldisilazane should be controlled in the above-mentioned scope, because, and when the content of heptamethyldisilazane is too high, can worsen the partial properties of electrolyte when the content of heptamethyldisilazane improves very little the time inoperatively to the performance of electrolyte.The mass percent of described film for additive and described non-aqueous organic solvent is 0.1%～5%.
Wherein, the chemical formula of described heptamethyldisilazane is:
The effect of described heptamethyldisilazane is the cycle performance that can significantly improve lithium ion battery, and makes that 60 ℃ of storages in 7 days of made lithium ion battery are functional.Thereby described heptamethyldisilazane can improve the cycle performance and the high temperature storage performance of lithium ion battery.Simultaneously, in conjunction with following formula:
Described non-aqueous organic solvent is evenly mixed by conventional base solvent and low melting point solvent, and the percent by volume of described conventional base solvent and low melting point solvent is 8%～40%: 92%～60%.Described conventional base solvent is one or both in ethylene carbonate, propene carbonate, dimethyl carbonate and the diethyl carbonate, described low melting point solvent is Methylethyl carbonic ester, methyl formate, methyl acetate, ethyl acetate, methyl butyrate and 1, one or more in the 2-dimethoxy-ethane.Described film for additive is a vinylene carbonate, 1, one or both in 3-propane sultone and the gamma-butyrolacton.
In addition, the lithium ion battery that the electrolyte of low temp lithium ion battery that a kind of utilization disclosed in this invention takes into account high-temperature behavior is made comprises positive pole, negative pole and barrier film, also comprises the electrolyte of low temp lithium ion battery of taking into account high-temperature behavior.
Embodiment 1
In the present embodiment, preparation is during electrolyte: earlier humidity less than 1% glove box in, is that 1: 1: 3 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate, methyl formate and Methylethyl carbonic ester according to volume ratio, in made non-aqueous organic solvent, add again respective quality by LiBF
4With the mixing lithium salts that LiBOB evenly mixes, being mixed with volume after evenly mixing is that 30ml and concentration are the mixing lithium salt solution of 1mol/L, wherein mixes LiBF in the lithium salts
4With the mol ratio of LiBOB be 8: 2; Simultaneously, in described mixing lithium salt solution, add earlier vinylene carbonate (VC) and add VC and the mass percent that is made between non-aqueous organic solvent is 2%, add again heptamethyldisilazane and add heptamethyldisilazane and the mass percent that is made between non-aqueous organic solvent is 1.0%, after treating that electrolytic salt (being described mixing lithium salts) fully dissolves, leave standstill 24h, promptly obtain taking into account the electrolyte of low temp lithium ion battery of high-temperature behavior.
When the electrolyte of low temp lithium ion battery of taking into account high-temperature behavior that utilization is mixed with is made lithium ion battery, should make the positive pole, negative pole and the barrier film that constitute lithium ion battery respectively, described barrier film is the celgard2320 barrier film.
When making positive pole, be solvent with N-dimethyl pyrrolidone (NMP), the active material that is adopted is modified porous spherical cobalt acid lithium (LiCoO
2), conductive agent is super conductive carbon black (Super P) and gas-phase growth of carbon fibre (VGCF), the mass percent of wherein adding NMP is between 40～65%.At first with NMP, LiCoO
2, Super P and VGCF be mixed with anode sizing agent according to design proportion, again the anode sizing agent for preparing is uniformly coated on the collector aluminium foil afterwards and drying, roll-in and die-cut after, just finish the making of positive plate.In the present embodiment, the mass percent of making used each raw material of anode sizing agent should be mutually: LiCoO
2: Super P: VGCF: PVDF (Kynoar): NMP=90%: 3%: 2%: 5%: 60%.
When making negative pole, be solvent with water, active material is MCMB, and conductive agent is super conductive carbon black (Super P), and bonding agent is the mixture of SBR and CMC, and the addition of water and the mass percent of above-mentioned solid matter content are between 90%～120%.Thereby preparation is during cathode size, with MCMB, Super P, SBR, CMC and H
2O is mixed with cathode size according to design proportion, again the cathode size for preparing is coated on afterwards on the copper foil of affluxion body and drying, roll-in and die-cut after, just finish the making of negative plate.In the present embodiment, the mass percent of making used each raw material of cathode size should be mutually: MCMB: Super P: SBR: CMC: H
2O=92%: 3%: 3%: 2%: 110%.
At last, die-cut good positive plate, negative plate and barrier film stacked gradually by the order of barrier film, negative plate, barrier film, positive plate, barrier film and negative plate from the bottom to top be combined into electric core, the electric core that is combined into utilizes aluminium pole ears and nickel lug to carry out ultrasonic bonding, the electric core that has welded is put in the aluminum-plastic packaged shell of square, with electric core after injecting the above-mentioned electrolyte of low temp lithium ion battery of taking into account high-temperature behavior for preparing and sealing behind 80 ℃ of baking 24h, just make battery size and be 552566 lithium ion battery, and the design capacity of battery is 800mAh.
Embodiment 2
In the present embodiment, as different from Example 1: preparation is during electrolyte: humidity less than 1% glove box in, is that 1: 2: 6 mixed is evenly made non-aqueous organic solvent with ethylene carbonate, ethyl acetate and Methylethyl carbonic ester according to volume ratio, in made non-aqueous organic solvent, add again respective quality by LiBF
4With the mixing lithium salts that LiBOB evenly mixes, being mixed with volume after evenly mixing is that 30ml and concentration are the mixing lithium salt solution of 1mol/L, wherein mixes LiBF in the lithium salts
4With the mol ratio of LiBOB be 9: 1; Simultaneously, in described mixing lithium salt solution, add 1 earlier, 3-propane sultone (PS) and add PS and the mass percent that is made between non-aqueous organic solvent is 2%, add again heptamethyldisilazane and add heptamethyldisilazane and the mass percent that is made between non-aqueous organic solvent is 0.5%, after treating that electrolytic salt fully dissolves, leave standstill 24h, promptly obtain taking into account the electrolyte of low temp lithium ion battery of high-temperature behavior.
In the present embodiment, utilize the manufacture method step of the electrolyte of low temp lithium ion battery making lithium ion battery of taking into account high-temperature behavior that is mixed with all identical with embodiment 1 with material requested.
Embodiment 3
In the present embodiment, as different from Example 1: preparation is during electrolyte: humidity less than 1% glove box in, is that 1: 2: 5 mixed is evenly made non-aqueous organic solvent with ethylene carbonate, methyl butyrate and Methylethyl carbonic ester according to volume ratio, in made non-aqueous organic solvent, add again respective quality by LiBF
4With the mixing lithium salts that LiBOB evenly mixes, being mixed with volume after evenly mixing is that 30ml and concentration are the mixing lithium salt solution of 1mol/L, wherein mixes LiBF in the lithium salts
4With the mol ratio of LiBOB be 9: 1; Simultaneously, in described mixing lithium salt solution, add earlier gamma-butyrolacton (GBL) and add GBL and the mass percent that is made between non-aqueous organic solvent is 3%, add again heptamethyldisilazane and add heptamethyldisilazane and the mass percent that is made between non-aqueous organic solvent is 0.5%, after treating that electrolytic salt fully dissolves, leave standstill 24h, promptly obtain taking into account the electrolyte of low temp lithium ion battery of high-temperature behavior.
In the present embodiment, utilize the manufacture method step of the electrolyte of low temp lithium ion battery making lithium ion battery of taking into account high-temperature behavior that is mixed with all identical with embodiment 1 with material requested.
Embodiment 4
In the present embodiment, as different from Example 1: preparation is during electrolyte: humidity less than 1% glove box in, is that 1: 1: 3 mixed is evenly made non-aqueous organic solvent with ethylene carbonate, propene carbonate and Methylethyl carbonic ester according to volume ratio, in made non-aqueous organic solvent, add again respective quality by LiBF
4With the mixing lithium salts that LiBOB evenly mixes, being mixed with volume after evenly mixing is that 30ml and concentration are the mixing lithium salt solution of 0.9mol/L, wherein mixes LiBF in the lithium salts
4With the mol ratio of LiBOB be 8: 1; Simultaneously, in described mixing lithium salt solution, add 1 earlier, 3-propane sultone (PS) and add PS and the mass percent that is made between non-aqueous organic solvent is 2%, add again heptamethyldisilazane and add heptamethyldisilazane and the mass percent that is made between non-aqueous organic solvent is 3.0%, after treating that electrolytic salt fully dissolves, leave standstill 24h, promptly obtain taking into account the electrolyte of low temp lithium ion battery of high-temperature behavior.
In the present embodiment, utilize the manufacture method step of the electrolyte of low temp lithium ion battery making lithium ion battery of taking into account high-temperature behavior that is mixed with all identical with embodiment 1 with material requested.
Embodiment 5
In the present embodiment, as different from Example 1: preparation is during electrolyte: humidity less than 1% glove box in, with ethylene carbonate, 1,2-dimethoxy-ethane and Methylethyl carbonic ester are that 1: 3: 8 mixed is evenly made non-aqueous organic solvent according to volume ratio, in made non-aqueous organic solvent, add again respective quality by LiBF
4With the mixing lithium salts that LiBOB evenly mixes, being mixed with volume after evenly mixing is that 30ml and concentration are the mixing lithium salt solution of 1.1mol/L, wherein mixes LiBF in the lithium salts
4With the mol ratio of LiBOB be 9: 2; Simultaneously, in described mixing lithium salt solution, add earlier vinylene carbonate (VC) and add VC and the mass percent that is made between non-aqueous organic solvent is 2%, add again heptamethyldisilazane and add heptamethyldisilazane and the mass percent that is made between non-aqueous organic solvent is 1.0%, after treating that electrolytic salt fully dissolves, leave standstill 24h, promptly obtain taking into account the electrolyte of low temp lithium ion battery of high-temperature behavior.
In the present embodiment, utilize the manufacture method step of the electrolyte of low temp lithium ion battery making lithium ion battery of taking into account high-temperature behavior that is mixed with all identical with embodiment 1 with material requested.
During actual fabrication, be the prepared good characteristic that goes out to take into account the electrolyte of low temp lithium ion battery of high-temperature behavior of checking the present invention, also done following three contrast tests simultaneously:
Contrast test one, humidity less than 1% glove box in, be that 1: 1: 3 mixed is even with ethylene carbonate, dimethyl carbonate and Methylethyl carbonic ester according to volume ratio, and add the LiPF of certain mass
6, be mixed with volume for 30ml concentration is the electrolyte of 1mol/L, add mass percent simultaneously and be 2% vinylene carbonate (VC), treat electrolytic salt LiPF
6Fully after the dissolving, leave standstill 24h, promptly obtain contrasting electrolyte one.
Contrast test two, humidity less than 1% glove box in, be that 1: 1: 3 mixed is even with ethylene carbonate, propene carbonate and Methylethyl carbonic ester according to volume ratio, and add the LiPF of certain mass
6, be mixed with volume for 30ml concentration is the electrolyte of 1mol/L, add mass percent simultaneously and be 2% 1,3-propane sultone (PS), treat that electrolytic salt fully dissolves after, leave standstill 24h, promptly obtain contrasting electrolyte two.
Contrast test three, humidity less than 1% glove box in, be that 1: 1: 3 mixed is even with ethylene carbonate, diethyl carbonate and Methylethyl carbonic ester according to volume ratio, and add the LiPF of certain mass
6, be mixed with volume for 30ml concentration is the electrolyte of 1mol/L, add mass percent simultaneously and be 2% vinylene carbonate (VC), treat that electrolytic salt fully dissolves after, leave standstill 24h, promptly obtain contrasting electrolyte three.
At first, five kinds of being made among the embodiment 1-5 are taken into account three kinds of electrolyte that make in the electrolyte of low temp lithium ion battery of high-temperature behavior and three contrast tests and carry out the test of normal temperature 1C cycle performance:
Tester: Neware charge-discharge test instrument;
Probe temperature: ambient temperature is a room temperature;
Charging modes: constant-current constant-voltage charging is to 4.2V, cut-off current 0.03CmA;
Discharge mode: constant-current discharge is to 3V;
Charging and discharging currents: 1.0C.
Draw finally that five kinds of being made among the embodiment 1-5 are taken into account the electrolyte of low temp lithium ion battery of high-temperature behavior and the cycle performance test result of three contrast test electrolyte sees Table 1:
Table 1 circulate electrolyte The performance test results contrast table
Secondly, five kinds of electrolyte of low temp lithium ion battery and three contrast test electrolyte of taking into account high-temperature behavior that made among the embodiment 1-5 are carried out the low temperature performance test:
Tester: climatic chamber;
Probe temperature: 0 ℃/-10 ℃-20 ℃/-30 ℃/-40 ℃/-50 ℃;
Charging modes: after room temperature left standstill 2h, constant-current constant-voltage charging was to 4.2V, cut-off current 0.03CmA;
Discharge mode: leave standstill 4h under probe temperature after, constant-current discharge is to 3V;
Charging and discharging currents: charging current is 1.0C, and discharging current is 0.2C.
Draw finally that five kinds of being made among the embodiment 1-5 are taken into account the electrolyte of low temp lithium ion battery of high-temperature behavior and the low temperature performance test result of three contrast test electrolyte sees Table 2:
Table 2 electrolyte temperature discharge performance test result contrast table
Then, three kinds of electrolyte of low temp lithium ion battery of taking into account high-temperature behavior that embodiment 1,2 and 3 is made carry out the test of low temperature high rate performance:
Probe temperature :-20 ℃/-30 ℃/-40 ℃;
Charging modes: after room temperature left standstill 2h, constant-current constant-voltage charging was to 4.2V, cut-off current 0.03CmA;
Discharge mode: leave standstill 4h under probe temperature after, constant-current discharge is to 3V;
Charging and discharging currents: charging current is 1.0C, and discharging current is 0.5C/1.0C.
Finally draw three kinds of low temperature high rate performance test results of taking into account the electrolyte of low temp lithium ion battery of high-temperature behavior that made in embodiment 1,2 and 3 and see Table 3:
Table 3 electrolyte low temperature high rate performance test result contrast table
Subsequently, five kinds of electrolyte of low temp lithium ion battery of taking into account high-temperature behavior that made among the embodiment 1-5 are carried out the high temperature discharge performance test:
Tester: climatic chamber;
Probe temperature: 55 ℃;
Charging modes: after room temperature left standstill 2h, constant-current constant-voltage charging was to 4.2V, cut-off current 0.03CmA;
Discharge mode: leave standstill 8h under probe temperature after, constant-current discharge is to 3V;
Charging and discharging currents: charging 1.0C/ discharge 0.2C.
Finally draw five kinds of high temperature discharge The performance test results of taking into account the electrolyte of low temp lithium ion battery of high-temperature behavior that made among the embodiment 1-5 and see Table 4:
Table 4 electrolyte high temperature discharge The performance test results contrast table
| Electrolyte | Discharge capacity/mAh of 55 ℃ | Discharge ratio/% | Middle threshold voltage/V |
| Embodiment 1 | ??808.8 | ??96.3 | ??3.809 |
| Embodiment 2 | ??811.5 | ??95.3 | ??3.798 |
| Embodiment 3 | ??789.9 | ??94.7 | ??3.802 |
| Embodiment 4 | ??785.1 | ??95.4 | ??3.802 |
| Embodiment 5 | ??782.1 | ??95.1 | ??3.800 |
At last, five kinds of electrolyte of low temp lithium ion battery of taking into account high-temperature behavior that made among the embodiment 1-5 are carried out the high temperature storage performance test:
Tester: thermostatic drying chamber;
Probe temperature: 60 ℃;
Shelve the time: 7 days.
Finally draw five kinds of high temperature storage The performance test results of taking into account the electrolyte of low temp lithium ion battery of high-temperature behavior that made among the embodiment 1-5 and see Table 5:
Table 5 electrolyte high temperature storage The performance test results contrast table
| Electrolyte | Conservation rate/% | Recovery rate/% | Internal resistance rate of change/% | Thickness change/% |
| Embodiment 1 | ??86.5 | ??95.2 | ??23.4 | ??1.6 |
| Embodiment 2 | ??83.6 | ??93.4 | ??20.8 | ??1.0 |
| Embodiment 3 | ??85.7 | ??94.3 | ??21.3 | ??0.8 |
| Embodiment 4 | ??86.2 | ??95.1 | ??22.4 | ??1.2 |
| Embodiment 5 | ??82.3 | ??92.1 | ??26.5 | ??1.1 |
Embodiment 6
In the present embodiment, as different from Example 1: preparation is during electrolyte: humidity less than 1% glove box in, is that 1: 1: 3 mixed is evenly made non-aqueous organic solvent with dimethyl carbonate, diethyl carbonate and Methylethyl carbonic ester according to volume ratio, in made non-aqueous organic solvent, add again respective quality by LiBF
4With the mixing lithium salts that LiBOB evenly mixes, being mixed with volume after evenly mixing is that 30ml and concentration are the mixing lithium salt solution of 0.8mol/L, wherein mixes LiBF in the lithium salts
4With the mol ratio of LiBOB be 24:1; Simultaneously, in described mixing lithium salt solution, add earlier by vinylene carbonate and 1, the 3-propane sultone is formed be mixed into film additive and to add the mass percent that is mixed into film additive and is made between non-aqueous organic solvent be 5%, add again heptamethyldisilazane and add heptamethyldisilazane mass percent be 0.1%, after treating that electrolytic salt fully dissolves, leave standstill 24h, promptly obtain taking into account the electrolyte of low temp lithium ion battery of high-temperature behavior.
In the present embodiment, utilize the manufacture method step of the electrolyte of low temp lithium ion battery making lithium ion battery of taking into account high-temperature behavior that is mixed with all identical with embodiment 1 with material requested.
Embodiment 7
In the present embodiment, as different from Example 1: preparation is during electrolyte: humidity less than 1% glove box in, is 1: 3: 3 with ethylene carbonate, methyl formate, ethyl acetate and Methylethyl carbonic ester according to volume ratio: 3 mixed is evenly made non-aqueous organic solvent, in made non-aqueous organic solvent, add again respective quality by LiBF
4With the mixing lithium salts that LiBOB evenly mixes, being mixed with volume after evenly mixing is that 30ml and concentration are the mixing lithium salt solution of 1.1mol/L, wherein mixes LiBF in the lithium salts
4With the mol ratio of LiBOB be 75: 15; Simultaneously, in described mixing lithium salt solution, add earlier vinylene carbonate and add vinylene carbonate and the mass percent that is made between non-aqueous organic solvent is 0.1%, add again heptamethyldisilazane and add heptamethyldisilazane mass percent be 7%, after treating that electrolytic salt fully dissolves, leave standstill 24h, promptly obtain taking into account the electrolyte of low temp lithium ion battery of high-temperature behavior.
In the present embodiment, utilize the manufacture method step of the electrolyte of low temp lithium ion battery making lithium ion battery of taking into account high-temperature behavior that is mixed with all identical with embodiment 1 with material requested.
Embodiment 8
In the present embodiment, as different from Example 1: preparation is during electrolyte: humidity less than 1% glove box in, is 4: 4: 40 with ethylene carbonate, diethyl carbonate, Methylethyl carbonic ester and methyl butyrate according to volume ratio: 52 mixed is evenly made non-aqueous organic solvent, in made non-aqueous organic solvent, add again respective quality by LiBF
4With the mixing lithium salts that LiBOB evenly mixes, being mixed with volume after evenly mixing is that 30ml and concentration are the mixing lithium salt solution of 1.1mol/L, wherein mixes LiBF in the lithium salts
4With the mol ratio of LiBOB be 88: 12; Simultaneously, in described mixing lithium salt solution, add earlier by vinylene carbonate and 1, the 3-propane sultone is formed be mixed into film additive and to add the mass percent that is mixed into film additive and is made between non-aqueous organic solvent be 4.5%, add again heptamethyldisilazane and add heptamethyldisilazane mass percent be 8%, after treating that electrolytic salt fully dissolves, leave standstill 24h, promptly obtain taking into account the electrolyte of low temp lithium ion battery of high-temperature behavior.
In the present embodiment, utilize the manufacture method step of the electrolyte of low temp lithium ion battery making lithium ion battery of taking into account high-temperature behavior that is mixed with all identical with embodiment 1 with material requested.
Embodiment 9
In the present embodiment, as different from Example 1: preparation is during electrolyte: humidity less than 1% glove box in, is 4: 4: 40 with ethylene carbonate, diethyl carbonate, ethyl acetate and methyl butyrate according to volume ratio: 52 mixed is evenly made non-aqueous organic solvent, in made non-aqueous organic solvent, add again respective quality by LiBF
4With the mixing lithium salts that LiBOB evenly mixes, being mixed with volume after evenly mixing is that 30ml and concentration are the mixing lithium salt solution of 1.2mol/L, wherein mixes LiBF in the lithium salts
4With the mol ratio of LiBOB be 73: 27; Simultaneously, in described mixing lithium salt solution, add earlier vinylene carbonate and add vinylene carbonate and the mass percent that is made between non-aqueous organic solvent is 4%, add again heptamethyldisilazane and add heptamethyldisilazane mass percent be 6%, after treating that electrolytic salt fully dissolves, leave standstill 24h, promptly obtain taking into account the electrolyte of low temp lithium ion battery of high-temperature behavior.
In the present embodiment, utilize the manufacture method step of the electrolyte of low temp lithium ion battery making lithium ion battery of taking into account high-temperature behavior that is mixed with all identical with embodiment 1 with material requested.
The above; it only is preferred embodiment of the present invention; be not that the present invention is imposed any restrictions, everyly any simple modification that above embodiment did, change and equivalent structure changed, all still belong in the protection range of technical solution of the present invention according to the technology of the present invention essence.
Claims (5)
1. electrolyte of low temp lithium ion battery of taking into account high-temperature behavior, form by the even mixed preparing of electrolytic salt, non-aqueous organic solvent, alkalinity additive and film for additive, it is characterized in that: the mixing lithium salts of described electrolytic salt for evenly mixing by LiBF4 and biethyl diacid lithium borate, and the mol ratio of LiBF4 and biethyl diacid lithium borate is 96～73: 4～27, and described electrolytic salt and the described non-aqueous organic solvent concentration of mixing lithium salt solution that forms that evenly is mixed is 0.8～1.2mol/L; Described alkalinity additive is a heptamethyldisilazane, and the mass percent of described heptamethyldisilazane and described non-aqueous organic solvent is 0.1%～8%; The mass percent of described film for additive and described non-aqueous organic solvent is 0.1%～5%.
2. according to the described electrolyte of low temp lithium ion battery of taking into account high-temperature behavior of claim 1, it is characterized in that: described non-aqueous organic solvent is evenly mixed by conventional base solvent and low melting point solvent, and the percent by volume of described conventional base solvent and low melting point solvent is 8%～40%: 92%～60%; Described conventional base solvent is one or both in ethylene carbonate, propene carbonate, dimethyl carbonate and the diethyl carbonate, described low melting point solvent is Methylethyl carbonic ester, methyl formate, methyl acetate, ethyl acetate, methyl butyrate and 1, one or more in the 2-dimethoxy-ethane.
3. according to claim 1 or the 2 described electrolyte of low temp lithium ion battery of taking into account high-temperature behavior, it is characterized in that: described film for additive is a vinylene carbonate, 1, one or both in 3-propane sultone and the gamma-butyrolacton.
4. a low temp lithium ion battery of taking into account high-temperature behavior that utilizes electrolyte according to claim 1 to make comprises positive pole, negative pole and barrier film, it is characterized in that: also comprise the electrolyte of low temp lithium ion battery of taking into account high-temperature behavior.
5. according to the described low temp lithium ion battery of taking into account high-temperature behavior of claim 4, it is characterized in that: described barrier film is the ce1gard2320 barrier film.
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| CN103560266A (en) * | 2013-11-07 | 2014-02-05 | 天津市捷威动力工业有限公司 | Long-service-life lithium ion battery and manufacture method thereof |
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