CN101394005A - Electrolysis liquid, lithium ionic cell containing the liquid and manufacturing method thereof - Google Patents
Electrolysis liquid, lithium ionic cell containing the liquid and manufacturing method thereof Download PDFInfo
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- CN101394005A CN101394005A CNA2007101530607A CN200710153060A CN101394005A CN 101394005 A CN101394005 A CN 101394005A CN A2007101530607 A CNA2007101530607 A CN A2007101530607A CN 200710153060 A CN200710153060 A CN 200710153060A CN 101394005 A CN101394005 A CN 101394005A
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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 provides non-aqueous electrolyte solution which comprises lithium salt, organic solvent and flame retardant additive, wherein the flame retardant additive is fluoro boric acid tri-ester. The invention further provides a lithium ion battery containing the electrolyte solution. The electrolyte solution provided by the invention has good flame retardance, and the lithium ion battery containing the electrolyte solution has better safety performance, high rate discharging performance and circulation capacity maintaining performance.
Description
Technical field
The present invention relates to a kind of electrolyte, contain the battery of this electrolyte and their preparation method, relate more specifically to a kind of nonaqueous electrolytic solution, contain the lithium ion battery of this electrolyte and their preparation method.
Background technology
Under the effect of the factors such as guiding of the breakthrough of the powerful demand of current portable electronic device market, new material new technology and application and national energy policy, lithium ion battery has obtained development at full speed because of having superior battery performance, it constantly substitutes ni-mh, cadmium nickel and lead-acid battery, and a few years just becomes the main source of secondary cell.
Secondary lithium battery uses the lithium oxide as positive active material usually, uses lithium metal, lithium alloy or crystallization or amorphous carbon material (as graphite, soft carbon, hard carbon etc.) as negative electrode active material.When the secondary lithium battery initial charge, lithium ion discharges from the lithium oxide positive active material of battery, is transferred to negative pole, and embeds in the negative pole in this.Because lithium has very high reactivity, can with the negative electrode active material qualitative response, generate lithia and lithium hydroxide etc., and then form organic solid electrolyte interface (SEI) film in negative terminal surface.In case form the SEI film, lithium ion just no longer with carbon negative pole or the reaction of other material, make the amount of lithium ion be maintained, and electrolyte no longer decomposes, so can keep stable charge and discharge cycles (J.Power Sources, 51 (1994), 79-104).
Yet, because the average discharge volt of secondary lithium battery is about the 3.6-3.7 volt, in order to produce high driving voltage, battery need stand 4 volts or higher voltage repeatedly when discharging and recharging, and the SEI film may break like this, lithium ion will continue to react with carbon negative pole or other material, electrolyte continues to decompose, along with the continuous minimizing of solvent, be settled out not dissolved salt and produce gas at negative pole, thereby inner pressure of battery is increased, battery structure is broken, even electrolyte may be revealed and on fire.In addition, exothermic reaction may take place in the frequent abuse of battery (as overcharge, short circuit, be heated, clashed), also may on fire even blast when the temperature of battery is higher than set point of temperature, and this on firely mainly cause by electrolyte.
At present, improving the most frequently used method of lithium ion battery security is to add flame-retardant additive in electrolyte, the adding of flame-retardant additive can make inflammable organic electrolyte become difficult combustion or non-flammable electrolyte, reduce battery heat release value and self-heating rate, also increase simultaneously the stability of electrolyte self, avoid burning or the blast of battery under overheated condition.At present research is more phosphate, phosphite ester, halogenated carboxylic ester and halogen ether.Wherein especially shown flame-retardant nature preferably with phosphate and phosphite ester compound, but these flame-retardant additives generally all have bigger viscosity, make the conductivity of electrolyte descend, thereby make the multiplying power discharging property and the circulation volume of the battery of the electrolyte preparation that contains such additive keep decreased performance.That is, can not take into account security performance and the multiplying power discharging property and the circulation volume maintenance performance of battery.
A kind of electrolyte that contains boric acid ester compound or its polymer is disclosed among the CN 1596260A, but the anti-flammability of this electrolyte is bad, conductivity is not high, and keeps performance not high with security performance, multiplying power discharging property and the circulation volume of the storage battery of this electrolyte preparation.
Summary of the invention
The objective of the invention is bad for the electrolyte flame-retardant that overcomes existing method preparation, conductivity is not high, security performance, multiplying power discharging property and the circulation volume of the battery that the electrolyte that makes with existing method is made keep the dissatisfactory defective of performance, a kind of good flame resistance, conductivity height are provided, and can significantly improve the nonaqueous electrolytic solution of security performance, multiplying power discharging property and the circulation volume maintenance performance of battery.
Second purpose of the present invention provides the preparation method of above-mentioned electrolyte.
The 3rd purpose of the present invention provides the lithium ion battery that contains this electrolyte.
The 4th purpose of the present invention provides the preparation method of above-mentioned lithium ion battery.
Electrolyte provided by the invention contains lithium salts, organic solvent and flame-retardant additive, and wherein, described flame-retardant additive is fluoro boric acid three esters.
The preparation method of electrolyte provided by the invention comprises that preparation contains the solution of lithium salts, organic solvent and flame-retardant additive, and wherein, described flame-retardant additive is fluoro boric acid three esters.
Lithium ion battery provided by the invention contains electricity level group and electrolyte, and described electrode group comprises positive pole, negative pole and the membrane layer 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 preparation positive pole and negative pole, and anodal, negative pole and the membrane layer between positive pole and negative pole are made electrode assemblie by coiling or lamination, then the electrode group is placed battery case, inject electrolyte, the sealed cell shell, wherein, described electrolyte is electrolyte provided by the invention.
The lithium ion battery that the electrolyte that fluoro boric acid three esters provided by the present invention are made as flame-retardant additive prepares, the reason that security performance is good is, at first, fluorine atom in fluoro boric acid three esters can be decomposed to form free radical when being heated, the borate structure also can form free radical simultaneously, this free radical can be caught hydroperoxyl radical or the hydroxyl free radical in the gas phase, thereby the chain reaction of the hydroxyl free radical when stoping burning, make the burning of organic electrolyte can't carry out or be difficult to carrying out, thereby improve the security performance of lithium ion battery; Secondly, the fluorine atom in the electrolyte component helps to form good SEI film at electrode interface.And in the preferred embodiment of the present invention, in electrolyte, having added film for additive, this film for additive also helps to form good SEI film at electrode interface, thereby further improves the security performance of lithium ion battery.
The lithium ion battery that the electrolyte that fluoro boric acid three esters provided by the present invention are made as flame-retardant additive prepares, multiplying power discharging property and circulation volume keep the good reason of performance to be, fluorine atom can weaken intermolecular viscous force, the moving resistance of molecule, ion is reduced, so, the electrolyte that the ratio of viscosities that contains the electrolyte of fluoro boric acid three esters contains the borate of fluoro not is low, thereby makes the multiplying power discharging property of battery and circulation volume keep performance to be significantly improved.
Embodiment
Electrolyte provided by the invention contains lithium salts, organic solvent and flame-retardant additive, and wherein, described flame-retardant additive is fluoro boric acid three esters.
Described fluoro boric acid three esters can be synthetic according to the synthetic method of routine, for example can reference literature J.Electrochem.Soc., and 1998,145 (8), 2813-2818 is by corresponding alcohol or phenol and BCl
3Reaction makes, and uses after the drying of purifying.
Under the preferable case, described fluoro boric acid three esters are fluoro boric acid three esters that structural formula is shown below:
Wherein, R
1, R
2And R
3Be selected from C
1-C
20Fluoro-alkyl, C
6-C
30Fluorinated aryl or hydrogen, R
1, R
2And R
3Can be identical or different, under the preferable case, R
1, R
2And R
3Identical, but R
1, R
2And R
3Be not hydrogen simultaneously.
Described fluoro-alkyl can be chain or ring-type fluoro-alkyl, and the carbon number of fluoro-alkyl is preferably 1-15, more preferably 1-6.Carbon number is that the example of the chain fluoro-alkyl of 1-6 can list methyl, ethyl, n-pro-pyl and isomers thereof, normal-butyl and isomers thereof, n-pentyl and isomers thereof or n-hexyl and the isomers thereof that diverse location is replaced by one or more fluorine atoms.The example of the isomers of n-pro-pyl comprises isopropyl; The example of the isomers of normal-butyl includes but not limited to isobutyl group, the tert-butyl group, sec-butyl; The example of the isomers of n-pentyl includes but not limited to isopentyl, neopentyl, 1,1-dimethyl propyl, 2-methyl butyl; The isomers of n-hexyl includes but not limited to 1-methyl amyl, 1-ethyl-butyl, 3-methyl amyl, isohesyl, new hexyl; Carbon number is that the ring-type fluoro-alkyl of 1-6 can be cyclopropyl, cyclobutyl, cyclopenta or the cyclohexyl that is replaced by one or more fluorine atoms.In described fluoro-alkyl, the replacement number of fluorine atom can be 1-13, is preferably 6-13.
Described fluorinated aryl can be the group with one or several fluoro aromatic rings, is preferably phenyl, naphthyl, indenyl, perylene base or xenyl that diverse location is replaced by one or more fluorine atoms, and this fluorinated aryl can have 0-4 and be selected from hydroxyl, C
1-C
10Fluoro-alkyl, nitro, cyano group and C
1-C
10The substituting group of alkoxyl.In described fluorinated aryl, the replacement number of fluorine atom can be 1-45, is preferably 9-30.
The consumption that is used as fluoro boric acid three esters of flame-retardant additive among the present invention is the 0.1-40 weight % of organic solvent, is preferably 5-20 weight %.
In the present invention, the electrolyte 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.Organic solvent serves as the migration medium of the ion that participates in electrochemical reaction.
Lithium salts of the present invention for example can be lithium hexafluoro phosphate (LiPF for well known to a person skilled in the art various lithium salts
6), LiBF4 (LiBF
6), hexafluoroarsenate lithium (LiAsF
6), lithium perchlorate (LiClO
4), trifluoromethyl sulfonic acid lithium (LiCF
3SO
3), perfluoro butyl sulfonic acid lithium (LiC
4F
9SO
3), lithium aluminate (LiAlO
4), chlorine lithium aluminate (LiAlCl
4), fluoro sulfimide lithium (LiN (C
xF
2x+1SO
2) (C
yF
2y+1SO
2) (x and y are positive integer in the formula)), in lithium chloride (LiCl) and the lithium iodide (LiI) one or more.The concentration of lithium salts is this area concentration commonly used, such as being the 0.5-2.0 mol, is preferably the 0.7-1.6 mol.
Organic solvent of the present invention comprises various high boiling solvents and low boiling point solvent.Specifically can list gamma-butyrolacton (GBL), ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), vinylene carbonate (VC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC), acid anhydrides, the N-methyl pyrrolidone, the N-methylformamide, the N-methylacetamide, acetonitrile, N, dinethylformamide, sulfolane, methyl-sulfoxide or dimethyl sulfite or other are fluorine-containing, sulfur-bearing or contain the ring-type organic ester of unsaturated bond, solvent of the present invention can be one or more in the above-mentioned solvent.In order to increase the solubility of lithium salts in solvent, the present invention preferably uses the mixed solvent of two kinds, three kinds or four kinds compositions in the above-mentioned solvent, the weight proportion of two kinds of solvents is 1:0.9-3.2, the weight proportion of three kinds of solvents is 1:1-1.5:0.2-1.5, and the weight proportion of four kinds of solvents is 1:1-1.7:0.1-1.2:0.2-0.9.The preferred ternary mixed solvent that uses ethylene carbonate, methyl ethyl carbonate and diethyl carbonate in the specific embodiment of the invention.
According to preferred embodiment provided by the present invention, be benchmark with 100 weight portion organic solvents, also contain film for additive 0.1-11 weight portion in the described electrolyte, preferred 2-8 weight portion.Described film for additive can be to well known to a person skilled in the art various additives, for example one or more in carbon dioxide, carbon disulfide, sulfur dioxide, vinylene carbonate (VC), ethylene sulfite (ES), propylene sulfite (PS) and the lithium carbonate.
The preparation method of electrolyte of the present invention comprises lithium salts, flame-retardant additive and film for additive is added in the organic solvent, stirs then to make it fully dissolve, be uniformly dispersed, and the gained clear liquid is electrolyte provided by the invention.Wherein, the addition sequence of lithium salts, flame-retardant additive and film for additive does not require, can add respectively, also can add simultaneously, but, when film for additive is gas such as carbon dioxide, sulfur dioxide, add other composition in the electrolyte earlier, usefulness-0.07MPa vacuumized 0.5-3 minute to the vacuum degree (vacuum degree is meant actual pressure and atmospheric difference) of-0.1MPa on the fluid injection machine again, then injecting carbon dioxide gas or sulfur dioxide gas gas.The amount of lithium salts, organic solvent, flame-retardant additive and film for additive makes that the concentration of lithium salts is the 0.1-2.0 mol, is preferably the 0.7-1.6 mol.
Secondary lithium battery of the present invention comprises the lithium ion battery of the various conventional materials of use 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 membrane layer 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 and 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 secondary lithium 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, 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, the concentration of for example 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 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) and 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, includes but not limited in 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 be 40-90 weight %, is preferably 50-85 weight %.
Described membrane layer 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 membrane layer can be the general various membrane layers 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 and will between described positive pole for preparing and the negative pole membrane layer be set, constitute the electrode group, this electrode group is contained in the battery case, inject electrolyte, then the battery case sealing can be made secondary lithium battery, wherein, described electrolyte is electrolyte provided by the invention.
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.
It is pure that all kinds of solvents of the present invention and reagent are analysis.
The following examples will the invention will be further described.
Embodiment 1
The synthetic method of flame-retardant additive boric acid three (to trifluoromethylbenzene) ester is as follows: the p-trifluoromethyl-phenol of 2.1 moles (340 gram) is dissolved in 2500 milliliters the anhydrous methylene chloride, under-78 ℃, slowly add the BCl of 700 milliliter of 1 mol by constant pressure funnel
3Hexane solution, whole dropping process is about 60 minutes, dropwise the back system and slowly be warming up to room temperature, stir about 12 hours under the room temperature then, reaction is finished the back and is removed by rotary evaporation and desolvate, and the residue that obtains is purified by decompression distillation, collect pressure and be 0.1 hold in the palm, temperature is the cut under 125-130 ℃ the condition, obtain product 124 grams, productive rate about 36%.
Product detects through NMR and is target product.
1H-NMR：(CDCl
3，ppm)6.7(m，6H)，7.8(m，6H)；
13C-NMR：(CDCl
3，ppm)：116.2，123.6，126.6，160.3。Confirm that the product of collecting is boric acid three (to a trifluoromethylbenzene) ester.
The preparation of electrolyte: in glove box, 100 gram (75.8 milliliters) ethylene carbonates, 100 gram methyl ethyl carbonates (100 milliliters) and 100 gram (102 milliliters) diethyl carbonates are mixed, to wherein adding 42 gram LiPF
6Electrolyte, restrain (about 11 milliliters to the film for additive vinylene carbonate (VC) that wherein adds 4.5 grams and 15 then, 5 weight % for organic solvent) flame-retardant additive---boric acid three (to trifluoromethylbenzene) ester is stirred to all solids material and all dissolves, and is made into the LiPF of 1 mol
6Solution promptly gets electrolyte of the present invention.
Anodal preparation: (Atuofeina Corp 761#PVDF) is dissolved in 1350 gram N-N-methyl-2-2-pyrrolidone N-(NMP) solvents and makes adhesive solution, adds 2895 gram LiCoO then in gained solution with 90 gram polyvinylidene fluoride
2(FMC Corp.'s commodity), fully mix and make anode sizing agent, it is on 20 microns the aluminium foil that this anode sizing agent is uniformly applied to thickness, and through 125 ℃ of dryings 1 hour, roll-in, cut-parts made 70 millimeters of 20 lengths of a film, wide 19 millimeters, thick 125 microns anode pole piece.The amount that applies makes every anode pole piece contain 6.3 gram LiCoO
2
The preparation of negative pole: with 30 gram CMC CMC (Jiangmen quantum Gao Ke company commodity, model is CMC1500) and 75 gram butadiene-styrene rubber (SBR) latex (Nantong Shen Hua chemical company commodity, the trade mark is TAIPOL1500E) be dissolved in the 1875 gram water, make adhesive solution, with 1395 gram graphite (SODIFF company commodity, the trade mark is DAG84) join in this adhesive solution, mix and make the graphite cathode slurry, this cathode size is coated on equably on the Copper Foil of 12 micron thickness and through 125 ℃ of dryings 1 hour, roll-in, cut-parts make 70 millimeters of 20 lengths of a film, wide 19 millimeters, thick 125 microns cathode pole piece.The amount that applies makes every cathode pole piece contain 3.1 gram graphite.
The preparation of battery: the polypropylene diaphragm of above-mentioned positive and negative plate and 20 micron thickness is wound into the rectangular lithium ion battery group, pack in the battery case and weld, subsequently the prepared electrolyte in front is injected in the battery case, 453450A type lithium rechargeable battery is made in sealing.
Embodiment 2
Prepare electrolyte and battery according to the method identical with embodiment 1, different is, as consumption 30 gram (22 milliliters are 10 weight % of organic solvent), the LiPF in the electrolyte that is made into of three pairs of trifluoromethyl phenyl esters of boric acid of flame-retardant additive
6Concentration be 0.9 mol.
Embodiment 3
Prepare electrolyte and battery according to the method identical with embodiment 1, different is, is 60 gram (45 milliliters are 20 weight % of organic solvent), LiPF in the electrolyte that is made into as the consumption of three pairs of trifluoromethyl phenyl esters of boric acid of flame-retardant additive
6Concentration be 0.9 mol.
Embodiment 4
Prepare electrolyte and battery according to the method identical with embodiment 1, different is, adopts boric acid three (the perfluor tert-butyl group) ester as flame-retardant additive, and its consumption is 15 gram (13 milliliters are 5 weight % of organic solvent), LiPF in the electrolyte that is made into
6Concentration be 1.0 mol;
Adopt the method identical to synthesize boric acid three (the perfluor tert-butyl group) ester with the synthetic method of embodiment 1 mesoboric acid three (to trifluoromethylbenzene) ester, different is, in the process of preparation boric acid three (the perfluor tert-butyl group) ester, p-trifluoromethyl-phenol with 2.1 moles of 2.1 moles perfluor tert-butyl alcohols replacements, during decompression distillation at last, collect pressure and be 7.5 holders, temperature and be the cut under 52-55 ℃ the condition, about 230 grams of product, productive rate about 46%.
Product is correct through the magnetic resonance detection structure,
13C-NMR:(CDCl
3, ppm) 106.2,93.7.Confirm that the product of collecting is boric acid three (the perfluor tert-butyl group) ester.
Embodiment 5
Prepare electrolyte and battery according to the method identical with embodiment 1, different is, is 30 gram (26 milliliters are 10 weight % of organic solvent), LiPF in the electrolyte that is made into as the consumption of boric acid three (the perfluor tert-butyl group) ester of flame-retardant additive
6Concentration be 0.9 mol.
Embodiment 6
Prepare electrolyte and battery according to the method identical with embodiment 1, different is, is 60 grams (51 milliliters, 20 weight % of organic solvent) as the consumption of boric acid three (the perfluor tert-butyl group) ester of flame-retardant additive, LiPF in the electrolyte that is made into
6Concentration be 0.8 mol.
Embodiment 7
Prepare electrolyte and battery according to the method identical with embodiment 1, different is, do not use film for additive, and employing boric acid three (3,5-two (trifluoromethyl) benzene) ester is as flame-retardant additive, addition is 15 gram (10.5 milliliters are 5 weight % of organic solvent), LiPF in the electrolyte that is made into
6Concentration be 1.0 mol;
Adopt the method identical to synthesize boric acid three (3 with the synthetic method of embodiment 1 mesoboric acid three (to trifluoromethylbenzene) ester, 5-two (trifluoromethyl) benzene) ester, different is, in the process of preparation boric acid three (3,5-two (trifluoromethyl) benzene) ester, with 2.1 moles 3,5-two (trifluoromethyl) phenol replaces 2.1 moles p-trifluoromethyl-phenol, during last decompression distillation, collects pressure and be 0.09 holder, temperature and be the cut under 126-130 ℃ the condition, get about 249 grams of product, productive rate about 51%.
Product is correct through the magnetic resonance detection structure,
1H-NMR (CDCl
3, ppm): 6.9 (m, 6H), 7.2 (s, 3H);
13C-NMR:(CDCl
3, ppm): 113.1,115.6,124.3,132.1,160.2.Confirm that the product of collecting is boric acid three (3,5-two (trifluoromethyl) benzene) ester.
Embodiment 8
Prepare electrolyte and battery according to the method identical with embodiment 1, different is not use film for additive, and as the boric acid three (3 of flame-retardant additive, 5-two (trifluoromethyl) benzene) consumption of ester is 30 gram (21 milliliters are 10 weight % of organic solvent), LiPF in the electrolyte that is made into
6Concentration be 0.9 mol.
Embodiment 9
Prepare electrolyte and battery according to the method identical with embodiment 1, different is not use film for additive, and as the boric acid three (3 of flame-retardant additive, 5-two (trifluoromethyl) benzene) consumption of ester is 60 gram (42 milliliters are 20 weight % of organic solvent), LiPF in the electrolyte that is made into
6Concentration be 0.9 mol.
Comparative Examples 1
Prepare electrolyte and battery according to the method identical with embodiment 1, different is that flame-retardant additive is the 30 gram (triphenyl borates of 24 milliliters are 10 weight % of organic solvent).
The flash-point of electrolyte, self-extinguishing time and conductivity test
Adopting instrument is the SBS-06 type flash point tester that the tall and sturdy Science and Technology Ltd. in east, Jilin Province produces, and measures the flash-point of embodiment 1-9 and Comparative Examples 1 prepared electrolyte with the agar diffusion method of remaining silent.Method of testing is as follows: the electrolyte of preparation is packed in the lubricating cup to the ring-shaped mark place, under continuous stirring, heat with very slow, constant speed, temperature interval in regulation, interrupt under the condition of stirring simultaneously, one flammule is introduced in the cup, minimum temperature when test flame causes steam scintillation on the sample is as close flash point, and each sample measurement is averaged for three times, and the result who records is as shown in table 1.
The test reference literature J.Electrochem.Soc. of self-extinguishing time, 2002,149 (5), A622-A626.Method is as follows: with mineral wool raw material being made diameter is 0.3-0.5 centimetre glass cotton balls, claims that its weight is m
1, then the glass cotton balls is placed in the electrolyte to be measured and fully soaks, take out and be weighed as m
2, the difference of the quality of glass cotton balls is the quality of cotton balls institute Electolyte-absorptive before and after soaking.This glass cotton balls is placed in front end is converted on the thin wire of " O " type and use the gas ignition device, the record igniter is removed the time T that extinguish automatically to flame afterwards the back, and this time is called self-extinguishing time SET (Self-extinguishing time).Obvious because cotton balls size and infiltration degree etc. can make cotton balls institute Electolyte-absorptive quality difference, thus can cause self-extinguishing time not have comparativity.And if be standard with the self-extinguishing time T ' of unit mass electrolyte, then can compare the fire resistance of different electrolytes fire retardant.The computing formula of T ' is as follows:
T’＝T/(m
2-m
1)
All self-extinguishing times all are meant the self-extinguishing time T ' of unit mass electrolyte among the present invention.Each sample in measurement is averaged for three times, and the result who records is as shown in table 1.
The 3173 type electric conductivity tester test implementations example 1-9 and the conductivity of Comparative Examples 1 prepared electrolyte under 25 ℃ that adopt Shanghai Ren Shi Electronics Co., Ltd. to produce, the result who records is as shown in table 1:
Table 1
From the data of table 1 as can be seen, adopt the electrolyte of method preparation of the present invention to compare with the electrolyte that adopts existing method preparation, flash-point height, the self-extinguishing time of the electrolyte of method preparation of the present invention is short, conductivity is high; And along with the increase of the content of flame-retardant additive, the electrolyte of method preparation of the present invention has correspondingly produced flash-point raising, self-extinguishing time shortens and conductivity improves effect.Thus, can illustrate that the flame retardant effect preferably of electrolyte provided by the invention and higher conductivity are the results of fluoro boric acid three ester effects, thereby good flame retardation effect, the conductivity height of the electrolyte of method preparation of the present invention have been described.
Battery performance test
The battery safety test
Will be with lithium battery test cabinet according to the battery of embodiment 1-9 and Comparative Examples 1 preparation with 1C constant-current constant-voltage charging 2.5 hours, be limited to 4.2V in the charging, and then battery crossed with 1C be charged to 5V, phenomenons such as whether the record battery occurs smoldering, burning, on fire, blast.Test result sees Table 2.
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative Examples 1 | |
| Phenomenon | Normally | Normally | Normally | Normally | Normally | Normally | Normally | Normally | End normal | Smolder |
By the data of table 2 as can be seen, adopt that smoldering does not appear in the battery of method preparation of the present invention, the phenomenon of on fire or blast under the 1C-5V overcharge conditions, illustrated that the battery of method preparation of the present invention can significantly improve the security performance of battery.
The multiplying power discharging volume test
Adopt BK6016 type secondary cell Performance Detection cabinet, the battery of the foregoing description 1-9 and Comparative Examples 1 preparation has been carried out the multiplying power discharging volume test, method of testing is: earlier with 1C (800mA) constant voltage charge to 4.2V, shelved 10 minutes; Be discharged to 3.0V with 5C (4000mA) then, shelved 10 minutes; Be discharged to 3.0V with 4C (3200mA), shelved 10 minutes; Be discharged to 3.0V with 3C (2400mA), shelved 10 minutes; Be discharged to 3.0V with 2C (1600mA), shelved 10 minutes; Be discharged to 3.0V with 1C (800mA), shelved 10 minutes; Be discharged to 3.0V with 0.5C (400mA), shelved 10 minutes; Be discharged to 3.0V with 0.2C (160mA); Discharge capacity when writing down current discharge with 5C, 4C, 3C, 2C, 1C, 0.5C and 0.2C respectively to 3.0V, data are as shown in table 3:
Table 3
By the data of table 3 as can be seen, even adopt the heavy-current discharge of the battery of method preparation of the present invention with 5C, about 50% when its discharge capacity still has 0.2C, part even be higher than 60%; And the battery that adopts existing method to prepare, the discharge capacity of its 5C only is 24.9% of 0.2C.Other is as the current discharge with 4C, 3C, 2C and 1C, for its discharge capacity discharge, the battery height that the battery that embodiment makes also makes than Comparative Examples.Illustrated that the battery of method preparation of the present invention can significantly improve the multiplying power discharging property of battery.
The cycle performance test
To carry out the cycle performance test according to the foregoing description 1-9 and Comparative Examples 1 prepared lithium ion battery.Method of testing is: battery is packed into battery on the secondary cell ability meter BS-9300 with correct method, earlier charge to 4.2V with the 1C constant-current constant-voltage charging, shelved 5 minutes, be discharged to 3.0V with 1C, charge to 4.2V with the 1C constant-current constant-voltage charging again, circulation is like this treated the capacity surplus ratio less than till 80%, writes down each circulation volume, the internal resistance of discharge attitude, middle threshold voltage etc.After the loop ends, treat that the battery temperature recovers normal temperature, be full of electricity, be discharged to 3.0V with 0.2C again, draw residual capacity, residual capacity is promptly got capability retention divided by circulation volume first with 1C.The gained result is as shown in table 4:
Table 4
From the data of table 4 as can be seen, adopt the battery of method preparation of the present invention to compare with the battery that adopts existing method preparation, circulate after 400 times, the capability retention of the battery of method preparation of the present invention is more than 80%, and the capability retention of the battery of Comparative Examples only is 67.0%, has illustrated that the battery of method preparation of the present invention can significantly improve the cycle performance of battery.
Claims (14)
1, a kind of nonaqueous electrolytic solution, this electrolyte contains lithium salts, organic solvent and flame-retardant additive, it is characterized in that, and described flame-retardant additive is fluoro boric acid three esters.
2, electrolyte according to claim 1, wherein, described fluoro boric acid three esters are fluoro boric acid three esters that structural formula is shown below:
Wherein, R
1, R
2And R
3Identical or different, be C
1-C
20Fluoro-alkyl or C
6-C
30Fluorinated aryl.
3, electrolyte according to claim 2, wherein, described fluoro-alkyl is that carbon number is chain or the ring-type fluoro-alkyl of 1-15; Described fluorinated aryl is the group with one or more fluoro aromatic rings.
4, electrolyte according to claim 3, wherein, the carbon number of described chain or ring-type fluoro-alkyl is 1-6; Methyl, ethyl, n-pro-pyl and isomers thereof, normal-butyl and isomers thereof, n-pentyl and isomers thereof or n-hexyl and the isomers thereof of described chain fluoro-alkyl for being replaced by one or more fluorine atoms, cyclopropyl, cyclobutyl, cyclopenta or the cyclohexyl of described ring-type fluoro-alkyl for being replaced by one or more fluorine atoms; Phenyl, naphthyl, indenyl, perylene base or the xenyl of described fluorinated aryl for being replaced by one or more fluorine atoms, described fluorinated aryl have 0-4 and are selected from hydroxyl, C
1-C
10Fluoro-alkyl, nitro, cyano group and C
1-C
10The substituting group of alkoxyl.
5, electrolyte according to claim 1, wherein, the amount of described flame-retardant additive is the 0.1-40 weight % of organic solvent, the content of described lithium salts is the 0.5-2.0 mol.
6, electrolyte according to claim 5, wherein, the amount of described flame-retardant additive is the 5-20 weight % of organic solvent, the content of described lithium salts is the 0.7-1.6 mol.
7, electrolyte according to claim 1, wherein, described electrolyte also contains film for additive, is benchmark with 100 weight portion organic solvents, and the content of film for additive is the 0.1-11 weight portion; Described film for additive is one or more in carbon dioxide, carbon disulfide, sulfur dioxide, vinylene carbonate, ethylene sulfite, propylene sulfite and the lithium carbonate.
8, a kind of preparation method of electrolyte, this method comprise lithium salts, organic solvent and flame-retardant additive are mixed, it is characterized in that described flame-retardant additive is fluoro boric acid three esters.
9, preparation method according to claim 8, wherein, described fluoro boric acid three esters are fluoro boric acid three esters that structural formula is shown below:
Wherein, R
1, R
2And R
3Identical or different, be C
1-C
20Fluoro-alkyl or C
6-C
30Fluorinated aryl.
10, preparation method according to claim 9, wherein, described fluoro-alkyl is that carbon number is chain or the ring-type fluoro-alkyl of 1-15; Described fluorinated aryl is the group with one or more fluoro aromatic rings.
11, preparation method according to claim 10, wherein, the carbon number of described chain or ring-type fluoro-alkyl is 1-6; Methyl, ethyl, n-pro-pyl and isomers thereof, normal-butyl and isomers thereof, n-pentyl and isomers thereof or n-hexyl and the isomers thereof of described chain fluoro-alkyl for being replaced by one or more fluorine atoms, cyclopropyl, cyclobutyl, cyclopenta or the cyclohexyl of described ring-type fluoro-alkyl for being replaced by one or more fluorine atoms; Phenyl, naphthyl, indenyl, perylene base or the xenyl of described fluorinated aryl for being replaced by one or more fluorine atoms, described fluorinated aryl have 0-4 and are selected from hydroxyl, C
1-C
10Fluoro-alkyl, nitro, cyano group and C
1-C
10The substituting group of alkoxyl.
12, preparation method according to claim 8, wherein, the amount of described flame-retardant additive is the 5-20 weight % of organic solvent, the content of described lithium salts is the 0.7-1.6 mol.
13, a kind of lithium ion battery, this battery comprises electrode group and electrolyte, and described battery pack comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, it is characterized in that, and described electrolyte is any described electrolyte among the claim 1-7.
14, a kind of preparation method of lithium ion battery, this method comprises preparation positive pole and negative pole and by coiling or lamination anodal, negative pole and the membrane layer between positive pole and negative pole is made the electrode group, then the electrode group is placed battery case, inject electrolyte, the sealed cell shell, it is characterized in that described electrolyte is any described electrolyte among the claim 1-7.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102315484A (en) * | 2011-08-30 | 2012-01-11 | 珠海汉格能源科技有限公司 | Overcharge resistant electrolyte of polymer lithium ion battery |
| CN102473963A (en) * | 2009-06-30 | 2012-05-23 | 旭硝子株式会社 | Electrolytic solution for chargeable device, electrolytic solution for lithium ion secondary battery, and secondary battery |
| CN104051784A (en) * | 2014-07-02 | 2014-09-17 | 东莞市凯欣电池材料有限公司 | Lithium secondary battery electrolyte, preparation method of lithium secondary battery electrolyte as well as lithium secondary battery |
| CN108376800A (en) * | 2018-02-02 | 2018-08-07 | 江苏海基新能源股份有限公司 | The electrolyte and lithium ion battery of high-temperature lithium ion battery cycle performance can be improved |
| CN109904515A (en) * | 2017-12-11 | 2019-06-18 | 宁德时代新能源科技股份有限公司 | Lithium ion secondary battery |
| CN113659200A (en) * | 2021-06-30 | 2021-11-16 | 厦门海辰新能源科技有限公司 | Electrolyte additive for improving high-temperature performance of lithium battery, electrolyte and electrochemical device |
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2007
- 2007-09-20 CN CNA2007101530607A patent/CN101394005A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102473963A (en) * | 2009-06-30 | 2012-05-23 | 旭硝子株式会社 | Electrolytic solution for chargeable device, electrolytic solution for lithium ion secondary battery, and secondary battery |
| CN102315484A (en) * | 2011-08-30 | 2012-01-11 | 珠海汉格能源科技有限公司 | Overcharge resistant electrolyte of polymer lithium ion battery |
| CN104051784A (en) * | 2014-07-02 | 2014-09-17 | 东莞市凯欣电池材料有限公司 | Lithium secondary battery electrolyte, preparation method of lithium secondary battery electrolyte as well as lithium secondary battery |
| CN109904515A (en) * | 2017-12-11 | 2019-06-18 | 宁德时代新能源科技股份有限公司 | Lithium ion secondary battery |
| CN108376800A (en) * | 2018-02-02 | 2018-08-07 | 江苏海基新能源股份有限公司 | The electrolyte and lithium ion battery of high-temperature lithium ion battery cycle performance can be improved |
| CN113659200A (en) * | 2021-06-30 | 2021-11-16 | 厦门海辰新能源科技有限公司 | Electrolyte additive for improving high-temperature performance of lithium battery, electrolyte and electrochemical device |
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