CN101442140A - Non-water electrolytic solution and preparation method thereof and lithium ion battery containing the same - Google Patents
Non-water electrolytic solution and preparation method thereof and lithium ion battery containing the same Download PDFInfo
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- CN101442140A CN101442140A CNA2007101880422A CN200710188042A CN101442140A CN 101442140 A CN101442140 A CN 101442140A CN A2007101880422 A CNA2007101880422 A CN A2007101880422A CN 200710188042 A CN200710188042 A CN 200710188042A CN 101442140 A CN101442140 A CN 101442140A
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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
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Abstract
The invention relates to a nonaqueous electrolyte. The electrolyte comprises lithium salts, an organic solvent and a silane compound, wherein the content of the silane compound is between more than 10 weight percent and 80 weight percent, the content of the lithium salts is between 0.5 and 20 weight percent, and the content of the organic solvent is between 3 and 85 weight percent by taking the total weight of the electrolyte as a reference; and the silane compound is one or more selected from silane compounds of which the boiling point is not less than 150 DEG C. The high-temperature safety performance of a battery prepared by the electrolyte is obviously improved.
Description
Technical field
The invention relates to a kind of electrolyte and preparation method thereof and the battery that contains this electrolyte, especially about a kind of nonaqueous electrolytic solution and preparation method thereof and the lithium ion battery that contains this electrolyte.
Background technology
Lithium rechargeable battery generally comprises battery container, electrode group and electrolyte, described electrode group and electrolyte are sealed in the battery container, described electrode group is by positive pole, barrier film and negative pole is reeled successively or stacked formation, in the positive pole with lithium-metal composite oxides as positive active material, in the negative pole with materials such as graphite, silicon as negative electrode active material, barrier film is used to separate positive pole and negative pole.Wherein, electrolyte is an important component part of battery, and the performance of battery is had a significant impact.
Along with constantly widening of lithium ion battery applications scope, market is also more and more higher to the lithium ion battery performance demands.At present, lithium rechargeable battery is mainly used in mobile phone and notebook computer.But seldom relate in other field, this mainly is because the cost of lithium rechargeable battery is higher, the cause that fail safe is relatively poor.Prior art improves the security performance in a certain respect of battery by adding certain additive, as over-charge safety performance or cycle performance and stability.
Disclose a kind ofly as CN1328355A, it is characterized in that described electrolyte comprises that at least a silane compound is as additive by being dissolved in the inorganic electrolyte salt that contains lithium in the aprotic solvent or containing the electrolyte that the organic electrolytic salt of lithium is formed.The concentration of additive is 0.1-5 weight % in electrolyte.The adding of described additive can improve the cycle performance and the stability of electrode.
CN1632984A discloses a kind of electrolyte of over charge preventing lithium ionic cell, it is characterized in that, in common lithium-ion battery electrolytes, add the trialkyl aryl-silane, and the addition of trialkyl aryl-silane is the 3-8 weight % of lithium-ion battery electrolytes weight.In the process that battery is overcharging, because lithium metal is deposited on anode and forms Li dendrite, pierces through barrier film easily, the positive and negative electrode of battery is directly contacted and the formation internal short-circuit, and influence the normal use of battery, and the adding of this silane compound can improve the performance of overcharging of battery.When battery overcharged, the temperature of battery generally was no more than 100 ℃.
Although above-mentioned additive can improve the cycle life of the over-charge safety performance or the battery of battery, but all can not effectively improve the high-temperature behavior of battery, promptly, battery still has the danger of blasting in hot environment, and also can cause other performance decrease of battery, as because the affiliation that adds of some additives makes cell expansion, shorten the cycle life of battery.
Especially with LiFePO
4As the lithium rechargeable battery of positive active material preparation, the high temperature safe performance of battery is still undesirable when using under hot environment.
Summary of the invention
The objective of the invention is for the electrolyte that overcomes lithium rechargeable battery in the prior art can not effectively improve and improve the hot relatively poor shortcoming of high temperature safe performance that makes battery of the stove of battery, provide a kind of battery stove that can effectively improve hot and make battery have the electrolyte of the lithium rechargeable battery of good high temperature safe performance.
Second purpose of the present invention provides the preparation method of above-mentioned electrolyte.
The 3rd purpose of the present invention provides the lithium rechargeable battery that contains this electrolyte.
The present inventor finds that the decomposition of the carbonate group organic solvent in the electrolyte of lithium-ion secondary battery during the SEI film forms can cause inside battery to produce H
2, CO, CO
2, CH
4, gas such as ethane, propane and propylene.In the charge and discharge process of battery, owing to the decomposition of electrolyte in the carbon negative terminal surface, the gas of generation increases the thickness of battery, causes the battery distortion, even safety problem that may be explosion caused, and is very big to the high temperature safe performance influence of battery.
The invention provides a kind of nonaqueous electrolytic solution, this nonaqueous electrolytic solution comprises lithium salts, organic solvent and silane compound, wherein, total weight with described electrolyte is a benchmark, the content of described silane compound is greater than 10 weight % to 85 weight %, the content of lithium salts is 0.5-20 weight %, and the content of organic solvent is 3-85 weight %; Described silane compound is selected from one or more in the silane compound that boiling point is not less than 150 ℃.
The preparation method of electrolyte provided by the invention comprises that preparation contains the solution of lithium salts, organic solvent and silane compound, wherein, it is benchmark that the consumption of each material makes the total weight with described electrolyte, the content of silane compound is greater than 10 weight % to 85 weight %, the content of lithium salts is 0.5-20 weight %, and the content of organic solvent is 3-85 weight %; Described silane compound is selected from one or more in the silane compound that boiling point is not less than 150 ℃.
The present invention also provides a kind of lithium rechargeable battery, this battery comprises electrode group and nonaqueous electrolytic solution, and described electrode group and nonaqueous electrolytic solution are sealed in the battery container, and described electrode group comprises positive pole, negative pole and barrier film, wherein, described electrolyte is electrolyte provided by the invention.
Adopt the high temperature safe performance of the battery that electrolyte provided by the invention prepares to obtain remarkable improvement, as the result of the battery stove thermal performance test of embodiment 14-26 as can be seen, battery A1-A13 is not all blasted and phenomenon on fire after placing 1 hour under 300 ℃ of high temperature, and at high temperature the time of Chu Cuning is longer, simultaneously, battery also has good electrochemical.Because lithium rechargeable battery provided by the invention contains above-mentioned electrolyte, thereby has the hot good advantage of battery stove, at high temperature has good security performance and stability.
Embodiment
Electrolyte provided by the invention comprises lithium salts, organic solvent and silane compound, wherein, is benchmark with the total weight of described electrolyte, and the content of described silane compound is greater than 10 weight % to 85 weight %.In order better to reach the requirement that improves battery safety, can not influence the charge and discharge performance of battery again, therefore, the content of silane compound of the present invention is greater than 10 weight % to 85 weight %, more preferably 15-75 weight %.Total weight with electrolyte is a benchmark, and the content of described lithium salts is 0.5-20 weight %, is preferably 5-15 weight %; The content of organic solvent is 3-85 weight %, is preferably 10-80 weight %.
According to the present invention, described silane compound is that boiling point is not less than 150 ℃, more preferably is not less than 250 ℃ silane compound, and under the preferable case, described silane compound is selected from (CH
3)
3SiO (CH
2CH
2O)
3CH
3, (CH
3)
2Si (O (CH
2CH
2O)
3CH
3)
2, (CH
3)
3Si (CH
2)
3O (CH
2CH
2O)
3CH
3, (CH
3)
3SiCH
2O (CH
2CH
2O)
3CH
3, CH
3CH
2SO
3Si (OCH
2CH
2OCH
3)
3And CH
3CH
2NH
2Si (OCH
2CH
2OCH
3)
3In one or more.When described silane compound was multiple mixture, its mixed proportion was not particularly limited, can mix by arbitrary proportion, as long as guarantee the content of silane compound be the electrolyte total weight greater than 10 weight %-80 weight %.Under the temperature of carrying out the furnace temperature test, and when situations such as battery overcharges, external short circuit, acupuncture, electrolyte provided by the invention all can generating gasification or decomposition, and the product that can dissolve the gasification of part carbonic ester or decompose, can effectively reduce cell internal pressure, reduce the potential safety hazard of battery explosion.
In the present invention, the dielectric in the electrolyte is a lithium salts, and lithium salts is provided by the source that provides of lithium ion in the battery, makes lithium ion battery can carry out basic operation.Non-aqueous organic solvent serves as the migration medium of the ion that participates in electrochemical reaction.
Lithium salts of the present invention can be a various lithium salts of the prior art, as lithium boron oxygen boron (LiBOB), 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, LiAlO
4, LiAsF
6, chlorine lithium aluminate (LiAlCl
4), lithium halide, as in lithium chloride (LiCl), lithium iodide (LiI) and the low fatty acid lithium carbonate one or more.For the conductibility that guarantees lithium ion and animal migration and guarantee the performance of electrolyte, generally speaking, the concentration of lithium salts is the 0.1-2.0 mol in the electrolyte, is preferably the 0.7-1.6 mol.
Non-aqueous organic solvent of the present invention can be the various organic solvents that are used for electrolyte well known in the art.Generally, described organic solvent can be ethylene sulfite (ES), propylene sulfite (PS), methyl sulfide (DMS), diethyl sulfite (DES), methyl formate (MF), methyl acrylate (MA), methyl butyrate (MB), ethyl acetate (EP), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC), other is fluorine-containing, sulfur-bearing or contain the chain organosilane ester of unsaturated bond, ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other are fluorine-containing, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond.
According to the present invention, described preparation method of electrolyte comprises that preparation contains the solution of lithium salts, organic solvent and silane compound, the preparation method of electrolyte of the present invention comprises lithium salts, silane compound and organic solvent mixed and obtains mixed solvent, heat 20-30 minute down with quick dissolving muddiness or precipitation at 50-80 ℃, the gained clear liquid is electrolyte provided by the invention.The order by merging of described lithium salts, silane compound and organic solvent is not particularly limited, and can random order mix, and under the preferable case, can earlier silane compound be mixed with organic solvent, and then add lithium salts.It is the 0.5-20 weight % of electrolyte total weight that the consumption of described lithium salts, silane compound and organic solvent makes the content of lithium salts in the electrolyte that obtains, and is preferably 5-15 weight %; The amount of silane compound be the electrolyte total weight greater than 10 weight % to 80 weight %, be preferably 15-75 weight %; The content of organic solvent is the 3-85 weight % of electrolyte total weight, is preferably 10-80 weight %.Generally, it is the 0.1-2.0 mol that the consumption of lithium salts makes the concentration of lithium salts in the electrolyte, is preferably the 0.7-1.6 mol.
Secondary lithium battery of the present invention comprises the lithium ion battery of various use conventional materials as active material.The same with prior art, secondary lithium battery provided by the invention comprises electrode group and electrolyte, and described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole.Because the present invention only relates to the improvement to prior art secondary lithium battery electrolyte, therefore other The Nomenclature Composition and Structure of Complexes to secondary lithium 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, 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).Under the preferable case, the phosphate metal lithium salts with olivine structural of described positive active material for representing: Li by following molecular formula
1+aL
bPO
4In the formula ,-0.1≤a≤0.2,0.9≤b≤1.1, L is at least a in iron, aluminium, manganese, cobalt, nickel, magnesium, zinc, the v element.Described positive active material is LiFePO 4 (LiFePO more preferably
4).According to the present invention, adopt by phosphate metal lithium salts such as LiFePO
4The improvement of the high temperature safe performance of the battery for preparing as the positive active material of lithium ion secondary battery positive electrode is more obvious, in addition, can also make battery in lower operating voltage, as operate as normal under the 3.8-2.0 volt, guarantee battery have good safety can in battery also have good electrochemical, as the discharge performance of big electric current.
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 secondary lithium battery.Can be selected from fluorine resin and/or polyolefin compound, as, one or more in polytetrafluoroethylene (PTFE), poly-two vinylidenes (PVDF) and the butadiene-styrene rubber.Weight with described positive active material is benchmark, and the content of described adhesive is 0.01-8 weight %, 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 conducting base and coating and/or is filled in negative material on the conducting base.Described conducting base 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), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols one or more.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 or negative electrode active material be 40-90 weight %, is preferably 50-85 weight %.
Described barrier film has electrical insulation capability and liquid retainability energy, is arranged between positive pole and the negative pole, and is sealed in the battery case with positive pole, negative pole and electrolyte.Described barrier film can be the general various barrier films 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 secondary lithium battery provided by the invention comprises positive pole, negative pole and barrier film is prepared into the electrode group, the electrode group and the electrolyte that obtain are sealed in the battery case, can make secondary lithium battery, wherein, described electrolyte is electrolyte provided by the invention.The injection rate of electrolyte is generally 1.5-4.9g/Ah, the concentration of electrolyte be generally 0.5-2.9 rub/liter.
The same with prior art, the preparation method of described positive pole is included on the positive electrode collector and applies the slurry that contains the conductive agent that positive active material, adhesive and selectivity contain, and promptly gets anodal after drying, roll-in, the section.Described drying is usually at 50-160 ℃, carries out under preferred 80-150 ℃.
The preparation method of negative pole is identical with anodal preparation method, just replaces containing the slurry of positive active material, adhesive and conductive agent with the slurry that contains negative electrode active material and adhesive.
Electrolyte provided by the invention can be applied to various lithium rechargeable batteries, and being specially adapted to by positive active material is the phosphate metal lithium salts as, LiFePO
4The lithium rechargeable battery for preparing.
The following examples will the invention will be further described.
Embodiment 1
Present embodiment is used to illustrate the preparation of electrolyte of the present invention and lithium rechargeable battery.
(1) preparation of electrolyte
Preparation electrolyte in the glove box (water content is less than 1ppm, and oxygen content is less than 0.1ppm) of applying argon gas: with mixed solvent and the 50 gram silane compound (CH of 36 gram vinyl carbonate: dimethyl carbonate=1:1 (weight ratio)
3)
3SiO (CH
2CH
2O)
3CH
3(Merck company is commercially available, and boiling point is 280 ℃) mixes, then to wherein adding 14 gram LiPF
6, after fully mixing, be mixed with the LiPF of 1.0 mol
6Solution is heated to solution and clarifies fully under 50 ℃, promptly get electrolyte of the present invention.Total weight with electrolyte is a benchmark, and the content of described silane compound is 50 weight %, and the total content of organic solvent is 36 weight %, and the content of lithium salts is 14 weight %.
(2) Zheng Ji preparation
With 94 weight portion LiFePO
4, 3 weight portion carbon blacks and 3 weight portion Kynoar (PVDF) mix with 65 weight portion N-N-methyl-2-2-pyrrolidone N-s (NMP) and make anode sizing agent, be coated in this anode sizing agent on the aluminium foil equably, then 130 ℃ of oven dry down, roll-in, cut-parts make and are of a size of long 478 millimeters * wide 42 millimeters * thick 124 microns positive pole, wherein contain 5.3 gram positive active material LiFePO
4
(3) preparation of negative pole
94 weight portion Delaniums and 6 weight portion adhesive Kynoar (PVDF) and 50 weight portion N-N-methyl-2-2-pyrrolidone N-s (NMP) are mixed make cathode size, be coated in this cathode size on the Copper Foil equably, then 130 ℃ of oven dry, roll-in, cut-parts make and are of a size of long 452 millimeters * wide 44 millimeters * thick 115 microns negative pole, wherein contain 2.6 gram negative electrode active material graphite.
(4) preparation of battery
Modified polypropene membrane coil coiled rectangular lithium ion battery group with above-mentioned positive pole, negative pole and 20 micron thickness, be encased in the battery case and weld, subsequently the above-mentioned electrolyte that makes is injected in the battery case, the injection rate of this electrolyte is 3.8g/Ah, and the lithium rechargeable battery A1 that model is LP053450A is made in sealing.
Embodiment 2
Present embodiment is used to illustrate the preparation of electrolyte of the present invention and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is that in the process of preparation electrolyte, used silane compound is (CH
3)
2Si (O (CH
2CH
2O)
3CH
3)
2(Merck company is commercially available, and boiling point is 250 ℃) makes lithium rechargeable battery A2.
Embodiment 3
Present embodiment is used to illustrate the preparation of electrolyte of the present invention and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is that in the process of preparation electrolyte, used silane compound is (CH
3)
3Si (CH
2)
3O (CH
2CH
2O)
3CH
3(Merck company is commercially available, and boiling point is 275 ℃) makes lithium rechargeable battery A3.
Embodiment 4
Present embodiment is used to illustrate the preparation of electrolyte of the present invention and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is that in the process of preparation electrolyte, used silane compound is (CH
3)
3SiCH
2O (CH
2CH
2O)
3CH
3(Merck company is commercially available, and boiling point is 230 ℃) makes lithium rechargeable battery A4.
Embodiment 5
Present embodiment is used to illustrate the preparation of electrolyte of the present invention and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is that in the process of preparation electrolyte, used silane compound is CH
3CH
2SO
3Si (OCH
2CH
2OCH
3)
3(Merck company is commercially available, and boiling point is 220 ℃) makes lithium rechargeable battery A5.
Embodiment 6
Present embodiment is used to illustrate the preparation of electrolyte of the present invention and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is that in the process of preparation electrolyte, used silane compound is CH
3CH
2NH
2Si (OCH
2CH
2OCH
3)
3(Merck company is commercially available, and boiling point is 265 ℃) makes lithium rechargeable battery A6.
Embodiment 7
Present embodiment is used to illustrate the preparation of electrolyte of the present invention and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is described silane compound (CH
3)
3SiO (CH
2CH
2O)
3CH
3Be respectively 15 grams and 71 with the consumption of the mixed solvent of vinyl carbonate and dimethyl carbonate and restrain (weight ratio of vinyl carbonate and dimethyl carbonate is 1:1), prepare electrolyte.Total weight with electrolyte is a benchmark, and the content of described silane compound is 15 weight %, and the total content of organic solvent is 71 weight %, and the content of lithium salts is 14 weight %.Make lithium rechargeable battery A7.
Embodiment 8
Present embodiment is used to illustrate the preparation of electrolyte of the present invention and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is described silane compound (CH
3)
3SiO (CH
2CH
2O)
3CH
3Be respectively 30 grams and 56 with the consumption of the mixed solvent of vinyl carbonate and dimethyl carbonate and restrain (weight ratio of vinyl carbonate and dimethyl carbonate is 1:1), prepare electrolyte.Total weight with electrolyte is a benchmark, and the content of described silane compound is 30 weight %, and the total content of organic solvent is 56 weight %, and the content of lithium salts is 14 weight %.Make lithium rechargeable battery A8.
Embodiment 9
Present embodiment is used to illustrate the preparation of electrolyte of the present invention and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is described silane compound (CH
3)
3SiO (CH
2CH
2O)
3CH
3Be respectively 40 grams and 46 with the consumption of the mixed solvent of vinyl carbonate and dimethyl carbonate and restrain (weight ratio of vinyl carbonate and dimethyl carbonate is 1:1), prepare electrolyte.Total weight with electrolyte is a benchmark, and the content of described silane compound is 40 weight %, and the total content of organic solvent is 46 weight %, and the content of lithium salts is 14 weight %.Make lithium rechargeable battery A9.
Embodiment 10
Present embodiment is used to illustrate the preparation of electrolyte of the present invention and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is described silane compound (CH
3)
3SiO (CH
2CH
2O)
3CH
3Be respectively 60 grams and 34 grams (weight ratio of vinyl carbonate and dimethyl carbonate is 1:1) with the consumption of the mixed solvent of vinyl carbonate and dimethyl carbonate, the consumption of lithium salts is 6 to restrain, and prepares electrolyte.Total weight with electrolyte is a benchmark, and the content of described silane compound is 60 weight %, and the total content of organic solvent is 34 weight %, and the content of lithium salts is 6 weight %.Make lithium rechargeable battery A10.
Embodiment 11
Present embodiment is used to illustrate the preparation of electrolyte of the present invention and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is described silane compound (CH
3)
3SiO (CH
2CH
2O)
3CH
3Be respectively 70 grams and 16 with the consumption of the mixed solvent of vinyl carbonate and dimethyl carbonate and restrain, prepare electrolyte.Total weight with electrolyte is a benchmark, and the content of described silane compound is 70 weight %, and the total content of organic solvent is 16 weight %, and the content of lithium salts is 14 weight %.Make lithium rechargeable battery A11.
Embodiment 12
Present embodiment is used to illustrate the preparation of electrolyte of the present invention and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is described silane compound (CH
3)
3SiO (CH
2CH
2O)
3CH
3Be respectively 80 grams and 10 grams with the consumption of the mixed solvent of vinyl carbonate and dimethyl carbonate, the consumption of lithium salts is 10 to restrain, and prepares electrolyte.Total weight with electrolyte is a benchmark, and the content of described silane compound is 80 weight %, and the total content of organic solvent is 10 weight %, and the content of lithium salts is 10 weight %.Make lithium rechargeable battery A12.
Embodiment 13
Present embodiment is used to illustrate the preparation of electrolyte of the present invention and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is that described silane compound is (CH
3)
3SiO (CH
2CH
2O)
3CH
3And CH
3CH
2SO
3Si (OCH
2CH
2OCH
3)
3Mixture, (CH
3)
3SiO (CH
2CH
2O)
3CH
3And CH
3CH
2SO
3Si (OCH
2CH
2OCH
3)
3Weight ratio be 2:1.Prepare electrolyte, and prepare lithium rechargeable battery A13.
Comparative Examples 1
This Comparative Examples is used to illustrate the preparation of reference electrolyte and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is that used silane compound is a disclosed trimethyl xenyl silane among the CN1632984A embodiment 1.Make reference lithium rechargeable battery B1.
Comparative Examples 2
This Comparative Examples is used to illustrate the preparation of reference electrolyte and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, different is, used silane compound is a disclosed trimethyl xenyl silane among the CN1632984A embodiment 1, and, the consumption of the mixed solvent of described silane compound and vinyl carbonate and dimethyl carbonate is respectively 5 grams and 81 and restrains, and is benchmark with the total weight of electrolyte, and the content of described silane compound is 5 weight %, the total content of organic solvent is 81 weight %, and the content of lithium salts is 14 weight %.Make reference lithium rechargeable battery B2.
Comparative Examples 3
This Comparative Examples is used to illustrate the preparation of reference electrolyte and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is described silane compound (CH
3)
3SiO (CH
2CH
2O)
3CH
3Being respectively 5 grams and 81 with the consumption of the mixed solvent of vinyl carbonate and dimethyl carbonate and restraining, is benchmark with the total weight of electrolyte, and the content of described silane compound is 5 weight %, and the total content of organic solvent is 81 weight %, and the content of lithium salts is 14 weight %.Make reference lithium rechargeable battery B3.
Comparative Examples 4
This Comparative Examples is used to illustrate the preparation of reference electrolyte and lithium rechargeable battery.
Method according to embodiment 1 prepares electrolyte and lithium rechargeable battery, and different is, does not contain silane compound in the described electrolyte, promptly directly the mixed solvents of 86 gram vinyl carbonate: dimethyl carbonate=1:1 (weight ratio) is restrained LiPF with 14
6Fully be hybridly prepared into the LiPF of 1.0 mol
6Solution is made reference lithium rechargeable battery B4 then.
Embodiment 14-26
The following example illustrates the performance test of the lithium ion battery A1-A13 that embodiment 1-13 is made.
1, battery capacity test
Under the room temperature condition, the battery of embodiment 1-13 preparation is lied prostrate with the current charges to 3.8 of 0.2C (120 milliamperes) respectively, rise to 3.8 volts of backs with constant-potential charge at voltage, cut-off current is 0.05C (30 milliamperes), after shelving 5 minutes, measure the capacity of battery, obtain battery capacity with 0.2C (120 milliamperes) current discharge to 2.0 volt.
Test result is as shown in table 1.
2, high temperature safe performance test
At room temperature, the battery that embodiment 1-13 is prepared lies prostrate with the current charges to 3.8 of 0.2C (120 milliamperes) respectively, rises to 3.8 volts of backs with constant-potential charge at voltage, and cut-off current is 0.05C (30 milliamperes), shelves 5 minutes; Carry out the test of 300 ℃ of stove heat.
Method of testing is: the nickel strap with one 0.15 * 4 * 50 millimeters of each spot welding of battery plus-negative plate requires spot welding firm; With the high temperature adhesive plaster thermocouple probe of digital display thermometer is fixed in the middle of the battery surface, then electricity is fixed on the thermocouple probe of digital display thermometer in the middle of the battery surface with the high temperature adhesive plaster, then battery is put into the approaching baking box of stove temperature and room temperature, with high temperature wire the battery plus-negative plate two ends are drawn with the positive and negative test pencil of universal instrument measuring voltage shelves in the baking box and link to each other.Open the power supply of air blast baking box again, this moment, electronic clock picked up counting, and made baking box rise to 300 ℃ with 5 ℃/minute programming rate, and stopped test after keeping 1 hour under this temperature; In opening power, pick up counting, temperature, cell voltage and furnace temperature every one minute record primary cell surface, the time that examines and write down the phenomenon that battery takes place (as: in the dead of night, smolder, phenomenon such as on fire or blast and battery heave deformation extent) and these phenomenons take place.
Test result is as shown in table 1.
Comparative Examples 5-8
Following Comparative Examples illustrates the performance test of the lithium ion battery B1-B4 that Comparative Examples 1-4 is made.
Method according to embodiment 14-26 is carried out performance test to battery, and different is the lithium ion battery B1-B4 of the battery of test for being made by Comparative Examples 1-4.
Test result is as shown in table 1.
Table 1
| The embodiment numbering | The battery numbering | Battery capacity (MAH) | The furnace temperature test |
| Embodiment 14 | A1 | 641 | The little drum of battery does not explode, and is not on fire |
| Embodiment 15 | A2 | 638 | The little drum of battery does not explode, and is not on fire |
| Embodiment 16 | A3 | 637 | The little drum of battery does not explode, and is not on fire |
| Embodiment 17 | A4 | 630 | The little drum of battery does not explode, and is not on fire |
| Embodiment 18 | A5 | 642 | The little drum of battery does not explode, and is not on fire |
| Embodiment 19 | A6 | 638 | The little drum of battery does not explode, and is not on fire |
| Embodiment 20 | A7 | 668 | The little drum of battery does not explode, and is not on fire |
| Embodiment 21 | A8 | 654 | The little drum of battery does not explode, and is not on fire |
| Embodiment 22 | A9 | 649 | The little drum of battery does not explode, and is not on fire |
| Embodiment 23 | A10 | 637 | The little drum of battery does not explode, and is not on fire |
| Embodiment 24 | A11 | 629 | The little drum of battery does not explode, and is not on fire |
| Embodiment 25 | A12 | 620 | The little drum of battery does not explode, and is not on fire |
| Embodiment 26 | A13 | 646 | The little drum of battery does not explode, and is not on fire |
| Comparative Examples 5 | B1 | 658 | Battery is on fire after placing 10 minutes, blast |
| Comparative Examples 6 | B2 | 647 | Battery is on fire after placing 6 minutes, blast |
| Comparative Examples 7 | B3 | 650 | Battery is on fire after placing 4 minutes, blast |
| Comparative Examples 8 | B4 | 642 | Battery is on fire after placing 1 minute, blast |
As can be seen from Table 1, compare with the battery B1-B4 that Comparative Examples 1-4 makes, the battery A1-A13 of embodiment 1-13 preparation is after placing 1 hour under 300 ℃ the high temperature, just swell a little of battery, and phenomenon on fire, blast does not take place, and reference cell B1-B4 is under 300 ℃ of high temperature, promptly occur after only placing in the short time on fire, explosion phenomenon.This shows, adopt the battery of electrolyte preparation provided by the invention to have good security performance, and the capacity of battery is still higher, illustrates that battery has good electrochemical simultaneously.
Claims (10)
1, a kind of nonaqueous electrolytic solution, this electrolyte contains lithium salts, organic solvent and silane compound, it is characterized in that, total weight with described electrolyte is a benchmark, the content of described silane compound is greater than 10 weight % to 80 weight %, the content of lithium salts is 0.5-20 weight %, and the content of organic solvent is 3-85 weight %; Described silane compound is selected from one or more in the silane compound that boiling point is not less than 150 ℃.
2, electrolyte according to claim 1 wherein, is benchmark with the total weight of described electrolyte, and the content of described silane compound is 15-75 weight %, and the content of lithium salts is 5-15 weight %, and the content of organic solvent is 10-80 weight %.
3, electrolyte according to claim 1 and 2, wherein, described silane compound is selected from (CH
3)
3SiO (CH
2CH
2O)
3CH
3, (CH
3)
2Si (O (CH
2CH
2O)
3CH
3)
2, (CH
3)
3Si (CH
2)
3O (CH
2CH
2O)
3CH
3, (CH
3)
3SiCH
2O (CH
2CH
2O)
3CH
3, CH
3CH
2SO
3Si (OCH
2CH
2OCH
3)
3And CH
3CH
2NH
2Si (OCH
2CH
2OCH
3)
3In one or more.
4, electrolyte according to claim 1, wherein, described lithium salts is selected from LiBOB, LiPF
6, LiBF
4, LiSbF
6, LiClO
4, LiCF
3SO
3, Li (CF
3SO
2)
2N, LiC
4F
9SO
3, LiAlO
4, LiAsF
6, LiAlCl
4, in LiCl, LiI and the low fatty acid lithium carbonate one or more.
5, electrolyte according to claim 1, wherein, described organic solvent is selected from one or more in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, dipropyl carbonate, ethylene carbonate, propene carbonate, vinylene carbonate, gamma-butyrolacton, sultone, ethylene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, methyl formate, methyl acrylate, methyl butyrate and the ethyl acetate.
6, the preparation method of the described electrolyte of claim 1, this method comprises that preparation contains the solution of lithium salts, organic solvent and silane compound, wherein, it is benchmark that the consumption of each material makes the total weight with described electrolyte, and the content of silane compound is greater than 10 weight % to 80 weight %; The content of lithium salts is 0.5-20 weight %, and the content of organic solvent is 3-85 weight %; Described silane compound is selected from one or more in the silane compound that boiling point is not less than 150 ℃.
7, method according to claim 6, wherein, it is benchmark that the consumption of each material makes the total weight with described electrolyte, and the content of described silane compound is 15-75 weight %, and the content of lithium salts is 5-15 weight %, and the content of organic solvent is 10-80 weight %.
8, according to claim 6 or 7 described methods, wherein, described silane compound is selected from (CH
3)
3SiO (CH
2CH
2O)
3CH
3, (CH
3)
2Si (O (CH
2CH
2O)
3CH
3)
2, (CH
3)
3Si (CH
2)
3O (CH
2CH
2O)
3CH
3, (CH
3)
3SiCH
2O (CH
2CH
2O)
3CH
3, CH
3CH
2SO
3Si (OCH
2CH
2OCH
3)
3And CH
3CH
2NH
2Si (OCH
2CH
2OCH
3)
3In one or more.
9, a kind of lithium rechargeable battery, this battery comprises electrode group and nonaqueous electrolytic solution, and described electrode group and nonaqueous electrolytic solution are sealed in the battery container, and described electrode group comprises positive pole, negative pole and barrier film, it is characterized in that described electrolyte is claim 1 or 2 described electrolyte.
10, battery according to claim 9, wherein, described positive pole comprises collector body and coating and/or is filled in positive electrode on the collector body, described positive electrode comprises positive active material, conductive agent and adhesive, the phosphate metal lithium salts with olivine structural of described positive active material for being represented by following molecular formula: Li
1+aL
bPO
4In the formula ,-0.1≤a≤0.2,0.9≤b≤1.1, L is at least a in iron, aluminium, manganese, cobalt, nickel, magnesium, zinc, the v element.
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| CN2007101880422A CN101442140B (en) | 2007-11-22 | 2007-11-22 | Non-water electrolytic solution and preparation method thereof and lithium ion battery containing the same |
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