CN1949581A - Electrolyte, lithium ion cell containing same and preparing process thereof - Google Patents
Electrolyte, lithium ion cell containing same and preparing process thereof Download PDFInfo
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- CN1949581A CN1949581A CNA2005101093540A CN200510109354A CN1949581A CN 1949581 A CN1949581 A CN 1949581A CN A2005101093540 A CNA2005101093540 A CN A2005101093540A CN 200510109354 A CN200510109354 A CN 200510109354A CN 1949581 A CN1949581 A CN 1949581A
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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 is an electrolyte, containing Li salt as electrolyte, organic solvent and additive, where the additive is selected from one or several of Li carbonate, Li sulfate, Li sulfite, Li nitrate, Li nitrite and Li aluminate. Thus, the overcharge safety and low temperature performance of a battery using the electrolyte containing inorganic matter additive are improved and there is no negative effect on the other performances of the battery, even obviously improved. And it not only enhances Li ion battery overcharge safety and improves the low temperature discharging performance, but also increases battery capacity, cycling performance, storage stability and reduces production cost.
Description
Technical field
The invention relates to a kind of electrolyte, contain the battery of this electrolyte and their preparation method, especially about a kind of nonaqueous electrolytic solution, the lithium ion battery that contains this electrolyte and their preparation method.
Background technology
Lithium ion battery is a kind of novel chemical power source, and energy density is big, operating voltage is high, the life-span is long, the characteristics of no environment public hazards because of it has, and is widely used in the portable type electronic products such as mobile phone.
Lithium ion battery comprises positive pole, negative pole, diaphragm paper and electrolyte.Described electrolyte comprises as electrolytical lithium salts, organic solvent and additive.Existing lithium ion battery uses organics additive to improve and overcharges fail safe or improve its cryogenic discharging characteristic.Organics additive is under the normal charge status of battery, to the work and the not influence of performance of battery; And when over-charging of battery, the meeting rapid polymerization improves the internal resistance of cell rapidly, is reduced to very little value fast by the electric current that makes battery, even approaches zero, thereby avoids the thermal decomposition of electrolyte and the rising of battery temperature, therefore plays a part to improve to overcharge fail safe.Low viscosity, subzero organic substance are added in the battery electrolyte as additive, can reduce the viscosity and the solidifying point of battery electrolyte integral body, thereby improve the low temperature performance of battery.
For example, CN 1385918A discloses a kind of electrolyte, contains for example 2-vinylpyridine of pyridines, biphenyl class or carbazoles highly reactive polymer monomer or its mixture in this electrolyte, thereby the fail safe that overcharges of battery is improved; The disclosed electrolyte of US6074776 and US6074777 is also by adding biphenyl class additive, and then the fail safe that overcharges that improves battery.
CN 1532986A discloses a kind of electrolyte, by adding solidifying point and all lower fluorobenzene of viscosity, thereby reduces the solidifying point and the viscosity of electrolyte, and then improves the low temperature performance of battery.
Although above-mentioned organic additive can both improve certain performance of battery, they improve a kind of performance as overcharge or cryogenic property in, other performance such as battery capacity, cycle life and bin stability descend on the contrary.As biphenyl class additive, though the fail safe that overcharges of battery is improved greatly, it can make cell expansion, shorten the cycle life of battery simultaneously, and reduce its low temperature performance, and must add the multiple expensive additive that other suppresses its negative effect again, cause cost very high.Therefore, need a kind of new additive that can overcome the defective of prior art organics additive, can improve over-charging of battery performance and low temperature performance, can keep or improve simultaneously other performance of battery again.
Summary of the invention
The electrolyte that the objective of the invention is to overcome lithium ion battery in the prior art can not be taken into account the shortcoming of over-charging of battery fail safe and low temperature performance simultaneously, and a kind of lithium-ion battery electrolytes that can improve over-charging of battery fail safe and low temperature performance simultaneously is provided.
Second purpose of the present invention provides the preparation method of this electrolyte.
The 3rd purpose of the present invention provides a kind of new lithium ion battery.
The 4th purpose of the present invention provides the preparation method of this lithium ion battery.
Electrolyte provided by the invention contains as electrolytical lithium salts, organic solvent and additive, wherein, described additive is selected from one or more of aluminate of the nitrite of nitrate, lithium of sulphite, the lithium of sulfate, the lithium of carbonate, the lithium of lithium and lithium.
The preparation method of electrolyte provided by the invention comprises and will mix as electrolytical lithium salts, organic solvent and additive, wherein, described additive is selected from one or more in the aluminate of the nitrite of nitrate, lithium of sulphite, the lithium of sulfate, the lithium of carbonate, the lithium of lithium and lithium.
Lithium ion battery provided by the invention comprises electrode group and electrolyte, and described electrode group comprises positive pole, negative pole and the diaphragm paper between positive pole and negative pole, and wherein, described electrolyte is electrolyte provided by the invention.
The preparation method of lithium ion battery provided by the invention comprises the electrode group for preparing battery, and this electrode group is contained in the battery container, injects electrolyte, the enclosed cell housing, and wherein, described electrolyte is electrolyte provided by the invention.
According to the present invention, select inorganic additive for use, replace organics additive of the prior art, in existing lithium-ion battery electrolytes in the aluminate of the nitrite of the nitrate of the sulphite of the sulfate of the carbonate of adding lithium, lithium, lithium, lithium, lithium and lithium one or more, not only strengthened the fail safe that overcharges of lithium ion battery, improved its low temperature performance, and improved battery capacity, prolonged battery cycle life, strengthened the bin stability of battery, also reduced production cost simultaneously.
Select industry lithium sulfate (Li for use as embodiment 8
2SO
3), lithium sulfate (Li
2SO
4) and lithium carbonate (Li
2CO
3) mixture as the additive preparation lithium ion battery, and comparative example 2 adopts biphenyl as the additive preparation lithium ion battery.Relatively every performance of two kinds of batteries as can be known: overcharging in the security test of 5 volts of voltage 2000 milliampere-hours, the swell phenomenon only appears in the both, and over-charge safety performance is all fine; Under-10 ℃ of cryogenic conditions, the ratio of the capacity when being discharged to 2.75 volts and discharge initial capacity with 1C, the former is 66.90%, and the latter is 44.97%, and the former low temperature performance is significantly better than the latter; The former exceeds 47.1 milliampere-hours than the latter by the average electrical capacity battery capacity test result; Behind the cycle charge-discharge 500 times, method of scoring survey battery circulation back varied in thickness the former 0.49 millimeter, 0.81 millimeter of the latter, the two capacitance conservation rate relatively, the former 81.45%, the latter 63.54%, comprehensive two indexs as can be known, the former cycle performance is better than the latter greatly; Store after 7 days for 60 ℃, the former reaches 88.8% the capacity restoration rate of survey battery, and the latter is 78.8%, illustrates that the former high-temperature storage stability is higher than the latter, and additive of the present invention does not bring negative effect at this aspect of performance.
Description of drawings
Fig. 1 is the battery outside drawing;
Fig. 2 is the graph of a relation of battery capacity conservation rate and cycle-index;
Fig. 3 is the thickness of battery in the loop test process and the graph of a relation of cycle-index.
Embodiment
Electrolyte provided by the invention contains as electrolytical lithium salts, organic solvent and additive, wherein, described additive is selected from one or more in the aluminate of the nitrite of nitrate, lithium of sulphite, the lithium of sulfate, the lithium of carbonate, the lithium of lithium and lithium.The carbonate of described lithium can be lithium carbonate and/or lithium bicarbonate; The sulfate of described lithium can be lithium sulfate and/or lithium hydrogen sulfate; The sulphite of described lithium is lithium sulfite and/or bisulfite lithium.
Total amount with electrolyte is a benchmark, and described content of additive is 0.1-5.0 weight %, is preferably 0.3-2.0 weight %.In general, described content of additive is high more, battery overcharge fail safe and low temperature performance is good more.Be lower than 0.1%, not obvious to the improvement of the every performance of battery; Be higher than 5.0%, inorganic salts are difficult to dissolving, and there is harmful effect in the difficulty that also becomes of fluid injection simultaneously to the cycle performance and the high-temperature storage stability of battery.
The present invention has no particular limits the particle diameter of described additive, can be the particle of various diameters, is preferably the particle below 25 microns, more preferably the 1-25 micron.Because described additive is an inorganic lithium salt, be insoluble in the organic solvent, therefore described additive exists with the solia particle state in electrolyte.All commercially available the getting of above-mentioned inorganic salts as additive also can prepare according to existing method.Unless stated otherwise, the inorganic salts as additive are commercially available analytical reagent described in the specific embodiment of the invention.
Of the present invention can be to be used as electrolytical various lithium salts in the lithium-ion battery electrolytes in the prior art as electrolytical lithium salts, as lithium hexafluoro phosphate (LiPF
6), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiSbF
6), lithium perchlorate (LiClO
4), fluorocarbon based sulfonic acid lithium (LiCF
3SO
3), Li (CF
3SO
2)
2N, LiC
4F
9SO
3, chlorine lithium aluminate (LiAlCl
4), LiN (C
xF
2x+1SO
2) (C
yF
2y+1SO
2) in (x and y are the natural number of 1-10 in the formula), lithium chloride (LiCl) and the lithium iodide (LiI) one or more.Concentration as electrolytical lithium salts in the electrolyte is generally the 0.1-2.0 mol, is preferably the 0.7-1.6 mol.
Described organic solvent can be a various high boiling solvent of the prior art, low boiling point solvent or their mixture, for example can be selected from gamma-butyrolacton, vinyl carbonate, the ethyl-methyl carbonic ester, dimethyl carbonate, diethyl carbonate, carbonic acid first propyl ester, dipropyl carbonate, propene carbonate, vinylene carbonate, sultone, and other is fluorine-containing, sulfur-bearing or contain the ring-type organosilane ester of unsaturated bond, organic acid anhydride, the N-methyl pyrrolidone, the N-methylformamide, the N-methylacetamide, acetonitrile, N, dinethylformamide, sulfolane, in the methyl-sulfoxide one or more.Organic solvent of the present invention is preferably in the above-mentioned solvent any two kinds, three kinds or four kinds of solvents by volume 1: (0.2-4) or 1: (0.2-4): (0.1-3) or 1: (0.3-2.5): (0.2-4): (0.1-4) mix the mixed solvent that obtains; It is the 0.1-2.0 mol that the addition of solvent makes as electrolytical lithium salt, is preferably the 0.7-1.6 mol.
The preparation method of electrolyte provided by the invention comprises and will mix as electrolytical lithium salts, organic solvent and additive, wherein, described additive is selected from one or more in the aluminate of the nitrite of nitrate, lithium of sulphite, the lithium of sulfate, the lithium of carbonate, the lithium of lithium and lithium.Total amount with electrolyte is a benchmark, and the addition of described additive is 0.1-5.0 weight %, preferred 0.3-2.0 weight %.
Although the described additive of various particle diameters can both be realized purpose of the present invention, under the preferable case, as the particle diameter of the inorganic salts of additive of the present invention below 25 microns.Therefore, preferably need carry out thinning processing to inorganic salts, the method of described thinning processing can be various thinning methods, for example can with as the inorganic salts of additive in ball mill with 100-250 rev/min of rotating speed ball milling 1-8 hour, just changeing 10 minutes earlier, reversed again 10 minutes, and so repeatedly, crossed the 200-400 mesh sieve behind the ball milling; Or additive ground 1-4 hour in mortar (as agate mortar), grind the back and cross the 200-400 mesh sieve.Two kinds of methods all can be controlled at the particle diameter of additive below 25 microns.
Described mixed method as electrolytical lithium salts, organic solvent and additive can be earlier organic solvent and additive to be mixed, and adds afterwards as electrolytical lithium salts again; Also can be to be dissolved in the organic solvent as electrolytical lithium salts earlier, behind the solution of formation homogeneous, more described additive be joined in the above-mentioned solution, obtain electrolyte provided by the invention.Owing to emitting a large amount of heat in the process that is dissolved into organic solvent as electrolytical lithium salts, make the electrolyte local temperature too high, additive is had a negative impact, therefore a kind of method in preferred back promptly will join in the organic solvent as electrolytical lithium salts earlier, form the solution of homogeneous, treat no longer heat release of system, when the gained solution temperature is reduced to ambient temperature, add described additive again, obtain electrolyte provided by the present invention.Under the preferable case, with the heating of gained electrolyte, so that described additive is uniformly dispersed in electrolyte solution.Described heating is preferably carried out under vacuum condition, and the temperature of heating can be 30-90 ℃, is preferably 40-60 ℃; The time of heating can be 2-24 hour, is preferably 3-8 hour.
Lithium ion battery provided by the present invention comprises electrode group and electrolyte, and described electrode group comprises positive pole, negative pole and the diaphragm paper between positive pole and negative pole, and wherein, described electrolyte is electrolyte provided by the invention.Because the present invention only relates to the improvement to the prior art lithium-ion battery electrolytes, therefore other The Nomenclature Composition and Structure of Complexes to lithium ion battery has no particular limits.
For example, described positive pole can be to well known to a person skilled in the art various positive poles, generally includes collector body and coating and/or is filled in positive electrode on this collector body.Described collector body can be a various collector body known in those skilled in the art, and as aluminium foil, Copper Foil, nickel plated steel strip etc., the present invention selects for use aluminium foil to make collector body.Described positive electrode can be a various positive electrode known in those skilled in the art, generally includes the conductive agent that positive active material, adhesive and selectivity contain, and described positive active material can be selected from the positive active material of lithium ion battery routine, as Li
xNi
1-yCoO
2(wherein, 0.9≤x≤1.1,0≤y≤1.0), Li
mMn
2-nB
nO
2(wherein, B is a transition metal, 0.9≤m≤1.1,0≤n≤1.0), Li
1+aM
bMn
2-bO
4(wherein ,-0.1≤a≤0.2,0≤b≤1.0, M is one or more in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur).
Positive electrode of the present invention has no particular limits adhesive, can adopt known in the art all can be used for the adhesive of lithium ion battery.Preferred described adhesive is the mixture of hydrophobicity adhesive and hydrophilic adhesive.The ratio of described hydrophobicity adhesive and hydrophilic adhesive has no particular limits, and can determine according to actual needs, and for example, the part by weight of hydrophilic adhesive and hydrophobicity adhesive can be 0.3: 1-1: 1.Described adhesive can use with the aqueous solution or emulsion form, also can use with solid form, preferably use with the aqueous solution or emulsion form, have no particular limits the concentration of described hydrophilic adhesive solution and the concentration of described hydrophobicity adhesive agent emulsion this moment, and the viscosity that can be coated with according to the slurry of positive pole that will prepare and cathode size and the requirement of operability are adjusted flexibly to this concentration.For example, the concentration of described hydrophilic adhesive solution can be 0.5-4 weight %, and the concentration of described hydrophobicity adhesive agent emulsion can be 10-80 weight %.Described hydrophobicity adhesive can be polytetrafluoroethylene, butadiene-styrene rubber or their mixture.Described hydrophilic adhesive can be hydroxypropyl methylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol or their mixture.The content of described adhesive is the 0.01-8 weight % of positive active material, is preferably 1-5 weight %.
Positive electrode provided by the invention can also optionally contain the common conductive agent that contains in the prior art positive electrode.Because conductive agent is used to increase the conductivity of electrode, reduce the internal resistance of battery, so the present invention preferably contains conductive agent.The content of described conductive agent and kind are conventionally known to one of skill in the art, for example, are benchmark with the positive electrode, and the content of conductive agent is generally 0-15 weight %, is preferably 0-10 weight %.Described conductive agent can be selected from one or more in conductive carbon black, acetylene black, nickel powder, copper powder and the electrically conductive graphite.
Consisting of of negative pole is conventionally known to one of skill in the art, and in general, negative pole comprises collector body and coating and/or is filled in negative material on the collector body.Described collector body is conventionally known to one of skill in the art, for example can be selected from aluminium foil, Copper Foil, nickel plated steel strip, the Punching steel strip one or more.Described negative active core-shell material is conventionally known to one of skill in the art, it comprises negative electrode active material and adhesive, described negative electrode active material can be selected from the negative electrode active material of lithium ion battery routine, as in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy one or more.Described adhesive can be selected from the adhesive of lithium ion battery routine, as in polyvinyl alcohol, polytetrafluoroethylene, CMC (CMC), the butadiene-styrene rubber (SBR) one or more.In general, the content of described adhesive is the 0.5-8 weight % of negative electrode active material, is preferably 2-5 weight %.
The solvent that is used to prepare anode sizing agent and cathode size of the present invention can be selected from conventional solvent, as being selected from N-methyl pyrrolidone (NMP), N, dinethylformamide (DMF), N, one or more in N-diethylformamide (DEF), methyl-sulfoxide (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can be coated on the described collector body described slurry and gets final product.In general, the consumption of solvent is that to make the concentration of positive active material in the slurries be 40-90 weight %, is preferably 50-85 weight %.
Described diaphragm paper has electrical insulation capability and liquid retainability energy, is arranged between positive pole and the negative pole, and is sealed in the battery container with positive pole, negative pole and electrolyte.Described diaphragm paper can be the general various diaphragm papers in this area, such as by those skilled in the art in the modified poly ethylene felt of respectively producing the trade mark, modified polypropene felt, ultra-fine fibre glass felt, vinylon felt or the nylon felt of known each manufacturer production and wettability microporous polyolefin film through welding or the bonding composite membrane that forms.
The preparation method of lithium ion battery provided by the invention, comprise between the positive pole for preparing battery and negative pole and positive pole that will prepare and the negative pole barrier film is set, constitute the electrode group, this electrode group is contained in the battery container, inject electrolyte, then that battery container is airtight, wherein, described electrolyte electrolyte provided by the invention.Except described electrolyte according to method provided by the invention prepare, the injecting electrolytic solution process carries out according to method provided by the invention, other step is conventionally known to one of skill in the art.In general, comprise the positive pole and the negative pole that prepare battery, and between positive pole that will prepare and the negative pole barrier film is set, constitute the electrode group, this electrode group is contained in the battery container, inject electrolyte, the enclosed cell housing, wherein, described electrolyte is electrolyte provided by the invention.Described injecting electrolytic solution mode can be for fluid injection machine fluid injection on the manually moving fluid injection of fluid injection tractor driver, the production line in glove box etc.In order to guarantee in the fluid injection process, described additive evenly distributes in electrolyte, and can uniform deposition after the fluid injection on negative terminal surface, injecting electrolytic solution described in the present invention preferably carries out under stirring condition, i.e. fluid injection while stirring.Described stirring is preferably magnetic agitation, and the speed of stirring is preferably 100-1000 rev/min.
The present invention is described further below in conjunction with embodiment.
Embodiment 1
Present embodiment illustrates electrolyte provided by the invention and contains the battery of this electrolyte and their preparation method.
(1) preparation of electrolyte
With 50 gram Li
2CO
3, in ball mill,, just changeing 10 minutes earlier with 150 rev/mins rotating speed ball milling 4 hours, reversed again 10 minutes, so repeatedly, ball milling 200 mesh sieves that finished obtain Li
2CO
3Powder.The gained powder is carried out results of grain size analysis to be shown: particle diameter is less than 1.562 microns Li
2CO
3Account for 10%, less than 3.983 microns Li
2CO
3Account for 50%, less than 22.24 microns Li
2CO
3Account for 95%.
At 210 milliliters of vinyl carbonates: ethyl-methyl carbonic ester: diethyl carbonate: dimethyl carbonate=2: 3: 1: in the mixed solvent of 1 (volume ratio), add 31.90 gram LiPF
6Be mixed with the solution of 1.0 mol; Left standstill 30 minutes, and treated that solution temperature was cooled to ambient temperature, to wherein adding the Li that 1.32 gram above-mentioned steps obtain
2CO
3Powder, afterwards under vacuum condition 40 ℃ the heating 12 hours, obtain inorganic additive Li
2CO
3Content is the electrolyte of 0.5 weight %.
(2) Zheng Ji preparation
30 gram polyvinylidene fluoride (PVDF) are dissolved in 450 gram N-methyl pyrrolidone (NMP) solvents make binder solution, the 940 gram LiCoO that will mix in advance then
2Join in the above-mentioned solution with 30 gram acetylene black powder, fully mix and make anode sizing agent; With tensile pulp machine this anode sizing agent is coated to thick 18 microns aluminium foil two sides equably, through 125 ℃ of vacuum and heating dryings 1 hour, roll-in, cut-parts make the positive pole of millimeter (wide) * 130,550 millimeters (length) * 43.8 micron (thick), contain the LiCoO that 7.9-8.1 restrains on the every positive pole
2
(3) preparation of negative pole
950 gram graphite, 20 gram carbon fibers and 30 gram butadiene-styrene rubber (SBR) are mixed.Adding 1500 milliliters water stirs and is made into cathode size, evenly be applied to 12 microns Copper Foil two sides with tensile pulp machine, through 125 ℃ of vacuum and heating dryings 1 hour, roll-in, cut-parts make the negative pole of millimeter (wide) * 130,515 millimeters (length) * 44.5 micron (thick), contain the graphite that 3.8-4.1 restrains on the every negative pole.
(4) assembling of battery
The above-mentioned positive pole that obtains, negative pole are wound into the electrode group of a square lithium ion battery with three layers of composite diaphragm of 20 microns polypropylene, polyethylene/polypropylene, and this electrode group included in 6 millimeters * 34 millimeters * 50 millimeters the rectangular cell aluminum hull, in glove box, in ar gas environment, manually inject about 2.8 milliliters of above-mentioned electrolyte, marginal not liquid limit magnetic stirrer in the fluid injection process, sealing, make lithium ion battery LP 063450, its design capacity is 1000 milliampere-hours.
Embodiment 2-8
Method according to embodiment 1 prepares electrolyte and lithium ion battery, the kind of the inorganic additive that different is adds, addition and be benchmark with the total amount of electrolyte, and the content of additive in electrolyte is as shown in table 1 below.
Table 1
| Embodiment | Additive | Addition (gram) | Content (weight %) |
| Embodiment 2 | Li 2CO 3 | 2.64 | 1.0 |
| Embodiment 3 | Li 2CO 3 | 5.28 | 2.0 |
| | Li 2SO 3 | 1.32 | 0.5 |
| Embodiment 5 | Li 2SO 3 | 2.64 | 1.0 |
| | Li 2SO 4 | 1.32 | 0.5 |
| | Li 2SO 4 | 2.64 | 1.0 |
| Embodiment 8 | Li 2CO 3 | 1.32 | 0.5 |
| Li 2SO 3 | 0.79 | 0.3 | |
| Li 2SO 4 | 0.79 | 0.3 |
Comparative example 1
The electrolyte of this comparative example explanation prior art and the preparation method of lithium ion battery.
Method according to embodiment 1 prepares electrolysis additive and lithium ion battery, different does not just add the additive that any raising overcharges fail safe, and does not stir in the electrolyte injection process.
Comparative example 2
The electrolyte of this comparative example explanation prior art and the preparation method of lithium ion battery.
Method according to embodiment 1 prepares electrolysis additive and lithium ion battery, and different is not add Li
2CO
3, but add 2.64 gram pressed powder organic substance biphenyl, and when making it be benchmark with electrolyte, concentration reaches 2.0 weight %, and does not stir in the electrolyte injection process as the additive that improves over-charge safety performance.
Battery performance test:
Battery with embodiment 1-8 and comparative example 1-2 prepare changes into the activation electrical property, and the cell voltage after changing into is not less than 3.85 volts.
(1) overcharges security test
In temperature is 16-30 ℃, and relative humidity is under the environmental condition of 20-85%, and the battery of embodiment 1-8 and comparative example 1-2 is overcharged security test.Method of testing is as follows:
Battery surface after cleaning changes into is discharged to 3.0 volts with battery with 1000 milliamperes.The output current in constant current constant voltage source transferred to overcharge test 1000 milliamperes of desired current values (1C) or 2000 milliamperes (2C), output voltage transfers to 5 volts, the thermocouple probe of thermometer is fixed on the middle place of battery side with the high temperature adhesive plaster, battery surface is evenly wrapped up the loose thick about 12 millimeters asbestos of one deck and when wrapping up asbestos is compacted to the 6-7 millimeters thick, close the power supply in constant current constant voltage source then, connect tested battery, universal instrument and constant current constant voltage source with lead, put to safety cabinet.Open the power supply in constant current constant voltage source, timing is simultaneously overcharged to battery, opens the universal instrument test voltage and changes; At any time write down temperature, voltage and the current variation of battery, observe simultaneously whether battery leakage, breach take place, is smoldered, blast, phenomenon on fire, the time that emphasis recording exceptional phenomenon takes place and the maximum temperature of battery surface at that time.The condition that termination overcharges test comprises: the battery surface temperature reaches more than 200 ℃; Battery explosion or on fire; Electric current drops to below 50 milliamperes when overcharging; Cell voltage reaches given voltage, and the battery surface temperature is lower than 40 ℃.
Meet under the prerequisite of above-mentioned termination test condition, when ending to overcharge test, described anomaly such as leakage, breach do not take place, smolder in tested battery, blast, on fire etc., are considered as by overcharging security test, otherwise are considered as not passing through.
Measurement result is as shown in table 2.
Table 2
| Electrolyte | The 1C-5 volt overcharges | The 2C-5 volt overcharges | ||
| Pass through situation | Phenomenon | Pass through situation | Phenomenon | |
| Embodiment 1 | By | Swell does not have blast, on fire | By | Swell does not have blast, on fire |
| Embodiment 2 | By | Swell does not have blast, on fire | By | Swell does not have blast, on fire |
| Embodiment 3 | By | Swell does not have blast, on fire | By | Swell does not have blast, on |
| Embodiment | ||||
| 4 | By | Swell does not have blast, on fire | By | Swell does not have blast, on fire |
| Embodiment 5 | By | Swell does not have blast, on fire | By | Swell does not have blast, on |
| Embodiment | ||||
| 6 | By | Swell does not have blast, on fire | By | Swell does not have blast, on |
| Embodiment | ||||
| 7 | By | Swell does not have blast, on fire | By | Swell does not have blast, on fire |
| Embodiment 8 | By | Swell does not have blast, on fire | By | Swell does not have blast, on fire |
| Comparative example 1 | Do not pass through | 92 minutes, 111 ℃ of blasts | Do not pass through | 51.5 divide 105 ℃ of blasts |
| Comparative example 2 | By | Swell does not have blast, on fire | By | Swell does not have blast, on fire |
From the result shown in the table 2 as can be seen, lithium ion battery provided by the invention overcharge fail safe, significantly better than the comparative example 1 that does not contain additive; Be on close level with the over-charge safety performance of comparative example 2 batteries that contain the electrolyte that adds organics additive.
(2) low temperature performance test
Under the environmental condition of relative humidity 20-85%, the battery of embodiment 1-8 and comparative example 1-2 is carried out the low temperature performance test.Method of testing is as follows:
With the battery after changing into after 1000 milliamperes of (1C) constant current charges to 4.2 volt, with 4.2 volts constant voltage charges, 100 milliamperes of charging initial currents, 20 milliamperes of cut-off currents charge.Be discharged to 3.0 volts with 1000 milliamperes then, measure the initial capacity that obtains battery discharge.And then with 1000 milliamperes of (1C) constant current charge to 4.2 volts; With 4.2 volts of constant voltage charges, 100 milliamperes of charging initial currents, 20 milliamperes of charging cut-off currents.After charging is finished, cooled off 30 minutes, and battery was put into-10 ℃ of climatic chambers, shelved 90 minutes, 1000 milliamperes are discharged to 2.75 volts, and are discharged to the discharge capacity of the cell of 3.1 volts, 3.0 volts and 2.75 volts with BS-9300 (R) secondary cell device for detecting performance fixed point record.Be calculated as follows the ratio of respectively fixing a point:
Each ratio of fixing a point=each fixed point capacity/initial capacity * 100%.
Measurement result is as shown in table 3.
Table 3
| Electrolyte and test condition | -10 ℃, the 1C discharge | ||||
| 3.1 volt fixed point ratio (%) | 3.0 volt fixed point ratio (%) | 2.75 volt fixed point ratio (%) | Middle threshold voltage (volt) | Stop internal resistance (milliohm) | |
| Embodiment 1 | 53.76 | 58.52 | 64.31 | 3.328 | 46.65 |
| Embodiment 2 | 56.97 | 62.66 | 69.50 | 3.348 | 46.10 |
| Embodiment 3 | 50.76 | 54.56 | 60.04 | 3.320 | 47.64 |
| | 53.80 | 58.80 | 64.80 | 3.301 | 46.00 |
| Embodiment 5 | 53.80 | 60.70 | 65.40 | 3.320 | 46.60 |
| | 51.70 | 57.00 | 62.10 | 3.297 | 46.70 |
| | 51.70 | 58.40 | 62.60 | 3.300 | 47.20 |
| Embodiment 8 | 52.60 | 59.10 | 66.90 | 3.330 | 46.30 |
| Comparative example 1 | 46.60 | 52.92 | 58.29 | 3.287 | 48.70 |
| Comparative example 2 | 34.06 | 39.28 | 44.97 | 3.213 | 50.37 |
From the result shown in the table 3 as can be seen, lithium ion battery provided by the invention has the low temperature performance that obviously is better than comparative example 2; Be on close level with the low temperature performance of comparative example 1 battery that does not add additive.
(3) battery capacity test
To the battery of embodiment 1-8 and comparative example 1-2, carry out the battery capacity test.Test environment is normal temperature, relative humidity 25-85%, and every kind of embodiment or comparative example are measured 15 batteries respectively.Assay method is as follows:
Use BS-9300 (R) secondary cell device for detecting performance is tested the battery after changing into, and battery is lied prostrate with 200 milliamperes of (0.2C) constant-current discharges to 3.0.Be calculated as follows capacitance:
Discharge capacity (milliampere-hour)=0.2C discharge capacity
Measurement result is as shown in table 4.
Table 4
| Capacity (milliampere-hour) | Embodiment 1 | Embodiment 2 | Embodiment 3 | | Embodiment 5 | | | Embodiment 8 | Comparative example 1 | Comparative example 2 |
| Battery 1 | 1100.0 | 1003.0 | 1072.0 | 1074.7 | 1042.0 | 1035.9 | 1022.0 | 1032.0 | 1044.0 | 1023.5 |
| Battery 2 | 1086.0 | 1057.0 | 1076.0 | 1070.0 | 1072.0 | 1052.5 | 1051.0 | 1061.0 | 1032.0 | 1011.8 |
| Battery 3 | 1097.0 | 1046.0 | 1062.0 | 1068.2 | 1059.0 | 1039.3 | 1038.0 | 1049.0 | 1046.0 | 1025.5 |
| | 1107.0 | 1097.0 | 1050.0 | 1066.9 | 1079.0 | 1043.2 | 1058.0 | 1069.0 | 1036.0 | 1015.7 |
| Battery 5 | 1071.0 | 1068.0 | 1081.0 | 1065.4 | 1080.0 | 1058.9 | 1059.0 | 1069.0 | 1051.0 | 1030.4 |
| | 1064.0 | 1092.0 | 1063.0 | 1052.9 | 1072.0 | 1046.2 | 1051.0 | 1062.0 | 1060.0 | 1039.2 |
| | 1118.0 | 1048.0 | 1062.0 | 1078.3 | 1060.0 | 1039.8 | 1039.0 | 1050.0 | 1045.0 | 1024.5 |
| Battery 8 | 1016.0 | 1094.0 | 1100.0 | 1048.7 | 1102.0 | 1079.0 | 1081.0 | 1092.0 | 1061.0 | 1040.2 |
| Battery 9 | 1058.0 | 1068.0 | 1043.0 | 1039.8 | 1061.0 | 1031.0 | 1051.0 | 1072.0 | 1071.0 | 1050.0 |
| Battery 10 | 1023.0 | 1095.0 | 1064.0 | 1033.7 | 1074.0 | 1047.6 | 1064.0 | 1085.0 | 1044.0 | 1023.5 |
| Battery 11 | 1099.0 | 1100.0 | 1068.0 | 1072.2 | 1090.0 | 1057.4 | 1073.0 | 1089.0 | 1026.0 | 1005.9 |
| Battery 12 | 1039.0 | 1094.0 | 1080.0 | 1049.5 | 1071.0 | 1054.0 | 1061.0 | 1082.0 | 1039.0 | 1018.6 |
| Battery 13 | 1084.0 | 1095.0 | 1050.0 | 1055.8 | 1078.0 | 1042.7 | 1068.0 | 1089.0 | 1008.0 | 988.24 |
| Battery 14 | 1032.0 | 1095.0 | 1023.0 | 1017.1 | 1060.0 | 1020.7 | 1050.0 | 1070.0 | 1002.0 | 982.35 |
| Battery 15 | 1014.0 | 1015.0 | 1010.0 | 1001.8 | 1018.0 | 993.72 | 1008.0 | 1028.0 | 1030.0 | 1009.8 |
| Average size | 1067.2 | 1071.0 | 1060.3 | 1053 | 1067.9 | 1042.8 | 1051.6 | 1066.4 | 1039.7 | 1019.3 |
From the result shown in the table 4 as can be seen, lithium ion battery provided by the invention all has the battery average size that is much higher than comparative example 2; For comparative example 1, lithium ion battery average size provided by the invention also obviously improves.
(4) cycle performance test
To the battery capacity of embodiment 1-8 and comparative example 1-2 preparation, under normal temperature, relative humidity 25-85% environmental condition, measure.Assay method is as follows:
At first, as shown in Figure 1, test top measurement point (4), middle part measurement point (5) and bottom measurement point (6) thickness of the battery sample after changing into respectively with vernier caliper.Wherein, described top measurement point is apart from (1) 5 millimeter of cover plate, apart from (2) 17 millimeters of sides; Described middle part measurement point is apart from (1) 25 millimeter of cover plate, apart from (2) 17 millimeters of sides; (3) 5 millimeters apart from the base of described bottom measurement points are apart from (2) 17 millimeters of sides.Use BS-9300 (R) secondary cell device for detecting performance to test then, after the battery after changing into is lied prostrate with 1000 milliamperes of (1C) constant current charges to 4.2, with 4.2 volts of constant voltage charges, 100 milliamperes of charging initial currents, 20 milliamperes of charging cut-off currents.Be discharged to 3.0 volts with 1000 milliamperes then, measure the initial capacity that obtains battery discharge.Circulation repeats with 1000 milliamperes of (1C) constant current charge to 4.2 volts; Be discharged to 3.0 volts charge and discharge process with 1000 milliamperes (1C) again, write down the 10th, 30,60,100,150,200,250,350,400,450,500 time loop ends capacity, and be calculated as follows the battery capacity conservation rate: capability retention=loop ends capacity/initial capacity * 100%.In addition, after circulation 100 times, 300 times and 500 times, use the vernier caliper measurement cell thickness, and the counting cell varied in thickness: cell thickness (millimeter) before varied in thickness (millimeter)=circulation back cell thickness (millimeter)-circulation.
The capability retention measurement result is as shown in table 5.
Table 5
| Cycle-index | Embodiment 1 | Embodiment 2 | Embodiment 3 | | Embodiment 5 | | | Embodiment 8 | Comparative example 1 | Comparative example 2 |
| 10 | 98.10 | 98.8 | 98.11 | 97.92 | 98.30 | 97.91 | 98.17 | 98.65 | 97.60 | 97.66 |
| 30 | 95.36 | 96.81 | 95.64 | 95.27 | 96.16 | 95.69 | 95.91 | 96.28 | 94.88 | 94.87 |
| 60 | 94.05 | 94.14 | 94.10 | 93.46 | 94.22 | 94.11 | 94.11 | 94.28 | 93.23 | 91.51 |
| 100 | 91.82 | 92.20 | 91.10 | 91.09 | 91.58 | 91.14 | 91.60 | 92.19 | 90.73 | 87.14 |
| 150 | 88.82 | 90.08 | 88.60 | 88.34 | 89.23 | 88.67 | 89.10 | 89.63 | 88.03 | 83.87 |
| 200 | 88.01 | 89.32 | 88.00 | 87.55 | 88.63 | 88.15 | 88.48 | 88.84 | 87.53 | 81.66 |
| 250 | 87.14 | 88.23 | 87.40 | 86.76 | 87.73 | 87.35 | 87.49 | 87.86 | 86.64 | 79.03 |
| 300 | 85.78 | 87.63 | 87.00 | 85.71 | 87.02 | 86.59 | 86.44 | 86.88 | 85.48 | 77.38 |
| 350 | 84.74 | 86.04 | 86.10 | 84.31 | 86.01 | 85.87 | 85.51 | 85.56 | 84.12 | 75.92 |
| 400 | 83.53 | 84.99 | 83.90 | 83.15 | 84.30 | 83.83 | 84.01 | 84.43 | 83.01 | 73.79 |
| 450 | 82.60 | 83.69 | 82.10 | 82.14 | 82.71 | 82.10 | 82.62 | 83.31 | 81.33 | 70.24 |
| 500 | 81.26 | 81.91 | 80.50 | 80.54 | 80.90 | 80.48 | 80.67 | 81.45 | 79.01 | 63.54 |
The cell thickness measurement result is as shown in table 6.
Table 6
| Scribing position | Before the circulation (micron) | After 100 times (micron) | 100 times thickness difference (micron) | After 300 times (micron) | 300 times thickness difference (micron) | After 500 times (micron) | 500 times thickness difference (micron) | |
| Embodiment 1 | Top | 6.19 | 6.28 | 0.09 | 6.56 | 0.37 | 6.68 | 0.49 |
| The middle part | 6.17 | 6.33 | 0.16 | 6.55 | 0.38 | 6.72 | 0.55 | |
| The bottom | 6.20 | 6.34 | 0.14 | 6.58 | 0.38 | 6.69 | 0.49 | |
| Average thickness | 6.19 | 6.32 | 0.13 | 6.53 | 0.37 | 6.65 | 0.50 | |
| Embodiment 2 | Top | 6.16 | 6.23 | 0.07 | 6.52 | 0.36 | 6.64 | 0.48 |
| The middle part | 6.12 | 6.28 | 0.16 | 6.51 | 0.39 | 6.67 | 0.55 | |
| The bottom | 6.16 | 6.29 | 0.13 | 6.53 | 0.37 | 6.64 | 0.48 | |
| Average thickness | 6.15 | 6.27 | 0.12 | 6.52 | 0.37 | 6.65 | 0.50 | |
| Embodiment 3 | Top | 6.19 | 6.29 | 0.10 | 6.55 | 0.36 | 6.66 | 0.47 |
| The middle part | 6.15 | 6.30 | 0.15 | 6.54 | 0.39 | 6.69 | 0.54 | |
| The bottom | 6.19 | 6.35 | 0.16 | 6.56 | 0.37 | 6.66 | 0.47 | |
| Average thickness | 6.18 | 6.31 | 0.14 | 6.55 | 0.37 | 6.67 | 0.49 | |
| Embodiment 4 | Top | 6.20 | 6.3 | 0.10 | 6.53 | 0.33 | 6.65 | 0.45 |
| The middle part | 6.17 | 6.31 | 0.14 | 6.54 | 0.37 | 6.67 | 0.50 | |
| The bottom | 6.19 | 6.33 | 0.14 | 6.56 | 0.37 | 6.68 | 0.49 | |
| Average thickness | 6.18 | 6.31 | 0.13 | 6.54 | 0.36 | 6.67 | 0.49 | |
| Embodiment 5 | Top | 6.18 | 6.29 | 0.11 | 6.54 | 0.36 | 6.69 | 0.51 |
| The middle part | 6.18 | 6.33 | 0.15 | 6.55 | 0.37 | 6.72 | 0.54 | |
| The bottom | 6.20 | 6.32 | 0.12 | 6.57 | 0.37 | 6.69 | 0.49 | |
| Average thickness | 6.19 | 6.31 | 0.12 | 6.55 | 0.36 | 6.70 | 0.51 | |
| Embodiment 6 | Top | 6.19 | 6.31 | 0.12 | 6.58 | 0.39 | 6.71 | 0.52 |
| The middle part | 6.17 | 6.32 | 0.15 | 6.55 | 0.38 | 6.75 | 0.58 | |
| The bottom | 6.19 | 6.34 | 0.15 | 6.59 | 0.40 | 6.71 | 0.52 | |
| Average thickness | 6.18 | 6.32 | 0.14 | 6.57 | 0.39 | 6.72 | 0.54 | |
| Embodiment 7 | Top | 6.19 | 6.30 | 0.11 | 6.57 | 0.38 | 6.7 | 0.51 |
| The middle part | 6.17 | 6.33 | 0.16 | 6.55 | 0.38 | 6.73 | 0.56 | |
| The bottom | 6.20 | 6.35 | 0.15 | 6.59 | 0.39 | 6.73 | 0.53 | |
| Average thickness | 6.19 | 6.33 | 0.14 | 6.57 | 0.38 | 6.72 | 0.53 | |
| Embodiment 8 | Top | 6.20 | 6.3 | 0.10 | 6.53 | 0.33 | 6.65 | 0.45 |
| The middle part | 6.17 | 6.31 | 0.14 | 6.54 | 0.37 | 6.67 | 0.50 | |
| The bottom | 6.19 | 6.33 | 0.14 | 6.56 | 0.37 | 6.68 | 0.49 | |
| Average thickness | 6.18 | 6.31 | 0.13 | 6.54 | 0.36 | 6.67 | 0.49 | |
| Comparative example 1 | Top | 6.21 | 6.26 | 0.05 | 6.58 | 0.37 | 6.79 | 0.58 |
| The middle part | 6.18 | 6.27 | 0.09 | 6.67 | 0.49 | 6.85 | 0.67 | |
| The bottom | 6.19 | 6.32 | 0.13 | 6.56 | 0.37 | 6.81 | 0.62 | |
| Average thickness | 6.19 | 6.28 | 0.09 | 6.60 | 0.41 | 6.82 | 0.63 | |
| Comparative example 2 | Top | 6.20 | 6.57 | 0.36 | 6.87 | 0.66 | 6.99 | 0.79 |
| The middle part | 6.19 | 6.62 | 0.43 | 6.86 | 0.66 | 7.03 | 0.84 | |
| The bottom | 6.20 | 6.63 | 0.43 | 6.88 | 0.68 | 7.00 | 0.79 | |
| Average thickness | 6.20 | 6.61 | 0.41 | 6.87 | 0.67 | 7.01 | 0.81 |
From table 5, table 6 and Fig. 2, result shown in Figure 3 as can be seen: lithium ion battery cycle performance provided by the invention is better than the battery of comparative example 2 greatly, the battery that contains inorganic additive electrolyte provided by the present invention, cycle performance obviously improves, and capacity still can remain on more than 80% after 500 circulations; The thickness increasing degree is very little before the battery circulation that contains inorganic additive electrolyte provided by the present invention in addition and in the process, and comparative example 2 cell thickness increases are quite big; The thickness increasing degree of comparative example 2 batteries is about 2 times of cell thickness increasing degree provided by the present invention.The battery of lithium ion battery provided by the invention and comparative example 1 compares, and cycle performance is suitable with it aspect capability retention; Aspect the cell thickness increasing degree, less than comparative example 1.
(5) high-temperature storage stability test
To the battery high-temperature bin stability of embodiment 1-8 and comparative example 1-2 preparation, measure.Assay method is as follows:
With the battery after changing into after 1000 milliamperes of (1C) constant current charges to 4.2 volt, with 4.2 volts constant voltage charges, 100 milliamperes of charging initial currents, 20 milliamperes of cut-off currents charge.Be discharged to 3.0 volts with 1000 milliamperes then, measure the initial capacity that obtains battery discharge, again battery is recharged to 4.2 volts with 1000 milliamperes (1C); Take off battery, cool off after 30 minutes, as shown in Figure 1, with middle part measurement point (5) detection cell thickness, internal resistance, the voltage of vernier caliper test battery sample; The baking box that battery is put into 60 ℃ was deposited 7 days; Take out battery and put normal temperature after 30 minutes, test battery is deposited internal resistance, middle part measurement point (5) thickness, voltage; Battery is discharged to 3 volts with 1000 milliamperes (1C), measures the storage capacity that obtains battery discharge.Again battery is lied prostrate with 1000 milliamperes of (1C) constant current charges to 4.2; Be discharged to 3.0 volts with 1000 milliamperes then, above-mentioned charge and discharge process 3 times is repeatedly measured last discharge process, obtains the recovery capacity of battery discharge.And then battery lied prostrate with 1000 milliamperes of (1C) constant current charges to 4.2; Take off battery normal temperature and place after 30 minutes, the recovery internal resistance of test battery, recovery thickness.Calculate self-discharge rate, capacity restoration rate and internal resistance rate of change by following formula:
Self-discharge rate=(initial capacity-storage capacity)/initial capacity * 100%
Capacity restoration rate=recovery capacity/initial capacity * 100%
Internal resistance rate of change=recovery internal resistance rising/initial internal resistance * 100%
7 days results are as shown in table 7 in 60 ℃ of storages.
Table 7
| The sharp condition of electrolyte | Voltage decline (volt) | Initial internal resistance (milliohm) | Store internal resistance rising (milliohm) | Recover internal resistance rising (milliohm) | Store thickness and increase (millimeter) | Recover thickness and increase (millimeter) | Self-discharge rate (%) | Capacity restoration rate (%) | Internal resistance rate of change (%) |
| Embodiment 1 | 0.07 | 39.0 | 7.4 | 8.7 | 0.46 | 0.15 | 15.1 | 89.0 | 22.3 |
| Embodiment 2 | 0.06 | 38.3 | 6.8 | 7.5 | 0.39 | 0.12 | 13.7 | 88.9 | 19.6 |
| Embodiment 3 | 0.07 | 39.3 | 8.0 | 8.8 | 0.40 | 0.10 | 13.6 | 86.8 | 22.4 |
| | 0.06 | 38.8 | 7.5 | 8.8 | 0.41 | 0.12 | 14.9 | 88.6 | 22.68 |
| Embodiment 5 | 0.06 | 39.5 | 7.5 | 8.3 | 0.41 | 0.10 | 14.7 | 88.6 | 21.0 |
| | 0.07 | 39.4 | 8.1 | 8.7 | 0.42 | 0.12 | 15.1 | 88.4 | 22.1 |
| | 0.07 | 39.2 | 7.6 | 8.9 | 0.42 | 0.12 | 15.4 | 88.2 | 22.7 |
| Embodiment 8 | 0.06 | 38.9 | 7.2 | 8.1 | 0.40 | 0.11 | 14.8 | 88.8 | 20.8 |
| Comparative example 1 | 0.08 | 39.7 | 8.4 | 9.5 | 0.49 | 0.17 | 15.9 | 85.9 | 23.9 |
| Comparative example 2 | 0.10 | 40.3 | 9.3 | 10.2 | 0.64 | 0.21 | 20.9 | 78.8 | 25.3 |
From the result shown in the table 7 as can be seen, 60 ℃ of stability of storing after 7 days down of lithium ion battery provided by the invention are higher than comparative example 2 far away, are higher than comparative example 1 simultaneously; The high-temperature storage stability that the battery that contains inorganic additive electrolyte provided by the present invention is described is fine.
The result of comprehensive above battery performance test as can be seen, use the battery that contains inorganic additive electrolyte provided by the invention, the over-charge safety performance and the cryogenic property of battery are improved simultaneously, and negative influence do not appear in other performances of battery yet, even obviously improve.Technical scheme of the present invention has not only strengthened the fail safe that overcharges of lithium ion battery, has improved its low temperature performance, and has improved capacity, cycle performance, the bin stability of battery, and has reduced production cost.
Claims (15)
1. electrolyte, this electrolyte contains as electrolytical lithium salts, organic solvent and additive, wherein, described additive is selected from one or more in the aluminate of the nitrite of nitrate, lithium of sulphite, the lithium of sulfate, the lithium of carbonate, the lithium of lithium and lithium.
2. electrolyte according to claim 1, wherein, described additive is selected from one or more in the sulphite of sulfate, lithium of carbonate, the lithium of lithium.
3. electrolyte according to claim 1 wherein, is benchmark with the total amount of electrolyte, and described content of additive is 0.1-5.0 weight %.
4. electrolyte according to claim 3 wherein, is benchmark with the total amount of electrolyte, and described content of additive is 0.3-2.0 weight %.
5. electrolyte according to claim 1, wherein, the particle diameter of described additive is the 1-25 micron.
6. electrolyte according to claim 1 wherein, describedly is selected from lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, lithium perchlorate, fluorocarbon based sulfonic acid lithium, Li (CF as electrolytical lithium salts
3SO
2)
2N, LiC
4F
9SO
3, in chlorine lithium aluminate, lithium chloride and the lithium iodide one or more, the concentration of described lithium salts is the 0.1-2.0 mol.
7. electrolyte according to claim 1, wherein, described organic solvent is selected from gamma-butyrolacton, vinyl carbonate, ethyl-methyl carbonic ester, dimethyl carbonate, diethyl carbonate, carbonic acid first propyl ester, dipropyl carbonate, propene carbonate, vinylene carbonate, sultone, organic acid anhydride, N-methyl pyrrolidone, N-methylformamide, N-methylacetamide, acetonitrile, N, one or more in dinethylformamide, sulfolane, the methyl-sulfoxide.
8. the preparation method of the described electrolyte of claim 1, this method comprises and will mix as electrolytical lithium salts, organic solvent and additive, wherein, described additive is selected from one or more in the aluminate of the nitrite of nitrate, lithium of sulphite, the lithium of sulfate, the lithium of carbonate, the lithium of lithium and lithium.
9. method according to claim 8, wherein, described hybrid mode as electrolytical lithium salts, organic solvent and additive will be for being dissolved in the organic solvent as electrolytical lithium salts earlier, form the solution of homogeneous, again additive is joined in the gained solution, obtain containing mixture as electrolytical lithium salts, organic solvent and additive.
10. method according to claim 9, wherein, this method comprises also the gained mixture is heated that the temperature of heating is 45-60 ℃ under vacuum condition, the time of heating is 2-24 hour.
11. method according to claim 8 wherein, is a benchmark with the total amount of electrolyte, described content of additive is 0.1-5.0 weight %.
12. method according to claim 8, wherein, the particle diameter of described additive is the 1-25 micron.
13. a lithium ion battery, this battery comprises electrode group and electrolyte, and described electrode group comprises positive pole, negative pole and the diaphragm paper between positive pole and negative pole, and wherein, described electrolyte is any described electrolyte among the claim 1-7.
14. the preparation method of the described lithium ion battery of claim 13, comprise between the positive pole for preparing battery and negative pole and positive pole that will prepare and the negative pole barrier film is set, constitute the electrode group, this electrode group is contained in the battery container, inject electrolyte, then that battery container is airtight, wherein, described electrolyte is any described electrolyte among the claim 1-7.
15. method according to claim 14, wherein, described electrolyte injects battery container under stirring condition.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324568A (en) * | 2011-09-15 | 2012-01-18 | 诺莱特科技(苏州)有限公司 | Electrolyte solution for improving swelling of lithium ion battery |
| CN104576081A (en) * | 2013-10-24 | 2015-04-29 | 中国科学院长春应用化学研究所 | Anti-freezing electrolyte solution and super capacitor |
| CN106025334A (en) * | 2015-03-31 | 2016-10-12 | 丰田自动车株式会社 | Lithium secondary battery and manufacturing method of the same |
| CN107706463A (en) * | 2017-11-23 | 2018-02-16 | 成都新柯力化工科技有限公司 | The nitroso grafting carbonic ester electrolyte and preparation method of a kind of lithium battery |
| CN109286042A (en) * | 2017-07-21 | 2019-01-29 | 天津金牛电源材料有限责任公司 | A kind of preparation method of electrolyte for lithium-ion power battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6350542B1 (en) * | 1999-01-25 | 2002-02-26 | Wilson Greatbatch Ltd. | Sulfite additives for nonaqueous electrolyte rechargeable cells |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102324568A (en) * | 2011-09-15 | 2012-01-18 | 诺莱特科技(苏州)有限公司 | Electrolyte solution for improving swelling of lithium ion battery |
| CN104576081A (en) * | 2013-10-24 | 2015-04-29 | 中国科学院长春应用化学研究所 | Anti-freezing electrolyte solution and super capacitor |
| CN104576081B (en) * | 2013-10-24 | 2017-11-14 | 中国科学院长春应用化学研究所 | Anti-condensation curable type electrolyte and ultracapacitor |
| CN106025334A (en) * | 2015-03-31 | 2016-10-12 | 丰田自动车株式会社 | Lithium secondary battery and manufacturing method of the same |
| CN106025334B (en) * | 2015-03-31 | 2018-11-06 | 丰田自动车株式会社 | Lithium secondary battery and its manufacturing method |
| CN109286042A (en) * | 2017-07-21 | 2019-01-29 | 天津金牛电源材料有限责任公司 | A kind of preparation method of electrolyte for lithium-ion power battery |
| CN109286042B (en) * | 2017-07-21 | 2020-11-10 | 天津金牛电源材料有限责任公司 | Preparation method of electrolyte for lithium ion power battery |
| CN107706463A (en) * | 2017-11-23 | 2018-02-16 | 成都新柯力化工科技有限公司 | The nitroso grafting carbonic ester electrolyte and preparation method of a kind of lithium battery |
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| CN100449855C (en) | Electrolyte, lithium ion cell containing same and preparing process thereof |
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Assignee: Huizhou Biyadi Industry Co., Ltd Assignor: Biyadi Co., Ltd. Contract fulfillment period: 2008.4.25 to 2012.11.19 contract change Contract record no.: 2008440000069 Denomination of invention: Electrolytic solution, lithium ion battery containing the same and their preparation method License type: General permission Record date: 2008.5.4 Assignee: Shenzhen BYD Lithium Battery Co., Ltd. Assignor: Biyadi Co., Ltd. Contract fulfillment period: 2008.4.25 to 2012.11.19 contract change Contract record no.: 2008440000071 Denomination of invention: Electrolytic solution, lithium ion battery containing the same and their preparation method License type: Exclusive license Record date: 2008.5.13 |
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Free format text: EXCLUSIVE LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.4.25 TO 2012.11.19 Name of requester: SHENZHEN BYD LITHIUM BATTERY CO., LTD. Effective date: 20080513 Free format text: COMMON LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.4.25 TO 2012.11.19 Name of requester: HUIZHOU BIYADI INDUSTRY CO.,LTD. Effective date: 20080504 |
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