CN101212062A - Non-aqueous electrolyte, Li-ion secondary battery, and method for producing them - Google Patents
Non-aqueous electrolyte, Li-ion secondary battery, and method for producing them Download PDFInfo
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- CN101212062A CN101212062A CNA2006101705908A CN200610170590A CN101212062A CN 101212062 A CN101212062 A CN 101212062A CN A2006101705908 A CNA2006101705908 A CN A2006101705908A CN 200610170590 A CN200610170590 A CN 200610170590A CN 101212062 A CN101212062 A CN 101212062A
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Abstract
The invention discloses non-water electrolyte, which contains lithium salt and organic solvent which are used as electrolyte. The electrolyte also contains aluminium sesquioxide; the particle diameter of the aluminium sesquioxide is 1-500 nanometers; as the total amount of the electrolyte is taken as the standard, the content of the aluminium sesquioxide is 0.1-20 per cent by weight. Through adding the nanometer level aluminium sesquioxide in the electrolyte in the invention, the cyclicity and safety performance of the battery are remarkably promoted; at the same time, the battery capacity and the high-temperature storage performance are also promoted in a certain degree.
Description
Technical field
The invention relates to a kind of electrolyte, contain the battery of this electrolyte and their preparation method, especially about a kind of nonaqueous electrolytic solution, the lithium rechargeable battery that contains this electrolyte and their preparation method.
Background technology
Recent two decades comes lithium ion battery to obtain development at full speed.As a kind of new forms of energy, lithium ion battery with its high voltage, high power capacity, low consumption, memory-less effect, nuisanceless, volume is little, specific energy is high, internal resistance is little, self-discharge rate is low, cycle-index is many, safe and reliable and volume outward appearance advantage such as variation arbitrarily, thereby from numerous batteries, show one's talent, receive more and more many people's concern, be widely used in electronics and IT products such as notebook computer, mobile phone.
Along with continuing to increase of lithium ion battery demand, the also raising day by day of requirement to its technology of preparing in the hope of making the more excellent battery product of higher, the various chemical property of energy density, better meets the demand in market.Wherein, the chemical properties such as capacity, cycle performance, security performance and high-temperature storage performance of raising lithium ion battery are the improved development trends of battery technology after reaching now.
Studies show that the main cause of degradation of cell performance is, when positive electrode is exposed in the electrolyte, electrolyte and positive electrode interact between the two, cause the dissolving of essential element in the positive electrode to be run off, thereby influence the various performances of battery.
At present, being used for solution to the problems described above has a lot.For example, JP 2001238692A is by adding lithium carbonate in positive active material, suppressing reaction anodal and electrolyte.But the adding of lithium carbonate can not form the protective layer of one deck densification on the positive active material surface, and positive active material still can react with electrolyte, and the adding of lithium carbonate also can reduce battery capacity.
In addition, human ZnO such as Y.-K.Sun is to LiNi
0.5Mn
1.5O
4Coat, the positive electrode of clading ZnO layer demonstrates high temperature cyclic performance (Electrochem Solid-State Lett, 2002,5 (5): A99-A102) very preferably.People such as Chen Jingbo make and coat LiCoO
2LiMn
2O
4, and the LiMn after finding to coat
2O
4Along with the increase of the covering amount of cobalt, initial specific capacity increases, and the cycle performance under normal temperature and the high temperature all has and improves (power technology .2003,27 (3): 284-286).
US2003148182 and CN1459131A suppress the reaction of positive active material and electrolyte, thereby improve the storge quality under cycle performance of battery and the high temperature by at positive active material surface clad oxide.
But, the chemical packs coating process complexity of said method, manufacturing cycle is long, and the cost height need carry out long high temperature sintering to coating and just can obtain coating layer or the constitutionally stable composite metal oxide that mixes the lithium that other metal is arranged.
Summary of the invention
The objective of the invention is provides the good nonaqueous electrolytic solution of a kind of cycle performance and security performance, contains the lithium rechargeable battery of this electrolyte and their preparation method in order to overcome the shortcoming of cycle performance in the prior art and poor safety performance.
The cycle performance of battery difference mainly contains the reason of two aspects: on the one hand be battery in cyclic process, dissolving takes place and runs off in positive active material, thereby causes cycle performance to descend; Be on the other hand since battery after the repeated charge process, the unit cell volume of positive active material increases, the binding energy between the structure cell reduces, the crystal structure order reduces, and is unfavorable for the embedding of lithium ion and disengages, thereby cause battery performance to descend.
The present inventor finds after deliberation, adds nano level alundum (Al in electrolyte, can significantly improve above-mentioned defective, especially can keep the stability of positive active material crystal structure in battery charge and discharge process.Nano level alundum (Al in the electrolyte can stably be dispersed in the electrolyte, when first charge-discharge, can form diaphragm on the positive active material surface, and simultaneously, the part alundum (Al also can react with positive active material, generates LiAl
xCo
1-xO
2Materials such as (0＜x＜1).By above-mentioned effect, can suppress the distortion that loss or crystal structure take place positive active material in the repeated charge process, can play the raising cycle performance of battery thereby can keep.
In addition, enter in the electrolyte low amounts of water can and the electrolyte lithium salt generation hydrofluoric acid of having an effect, hydrofluoric acid can produce SEI film and positive electrode and corrode, and cause reductions such as battery capacity and security performance.The present invention passes through to add nano level alundum (Al in electrolyte, by the effect of alundum (Al and water, thus the generation of inhibition hydrofluoric acid, the security performance of raising battery and battery capacity etc.
The invention provides a kind of nonaqueous electrolytic solution, this electrolyte contains as electrolytical lithium salts and organic solvent, wherein, also contain alundum (Al in this electrolyte, the particle diameter of described alundum (Al is the 1-500 nanometer, total amount with electrolyte is a benchmark, and the content of described alundum (Al is 0.1-20 weight %.
The preparation method of nonaqueous electrolytic solution provided by the invention, this method comprises lithium salts and organic solvent is mixed, obtain nonaqueous electrolytic solution, wherein, this method also is included in the described nonaqueous electrolytic solution and adds alundum (Al, mixes, and the particle diameter of described alundum (Al is the 1-500 nanometer, total amount with electrolyte is a benchmark, and the content of described alundum (Al is 0.1-20 weight %.
The present invention also provides a kind of lithium rechargeable battery, comprise electrode group and electrolyte, described electrode group and electrolyte are sealed in the battery case, and described electrolysis group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, wherein, described electrolyte is electrolyte provided by the invention.
The preparation method of lithium rechargeable battery provided by the invention, this method comprises positive pole and the negative pole for preparing this battery, and positive pole, negative pole and the barrier film between positive pole and negative pole are prepared into pole piece, then pole piece is placed battery case, inject electrolyte, the sealed cell shell, wherein, described electrolyte is electrolyte provided by the invention.
The present invention has significantly improved the cycle performance and the security performance of battery by add nano level alundum (Al in electrolyte, simultaneously, the raising of battery capacity and high-temperature storage performance is also improved.For example, use battery that electrolyte of the present invention makes after 400 circulations, discharge capacitance is all more than 75%, and the battery that prior art makes only is 62.0%.The battery that the present invention makes stable performance under the condition of overcharging does not produce dangerous phenomenons such as blast.In addition, the self-discharge rate of the battery that the present invention makes is all below 25%, and the capacity restoration rate is all more than 85%, and the self-discharge rate of the battery that prior art makes is up to 30.65%, and the capacity restoration rate only is 79.26%.
In addition, the preparation method of electrolyte of the present invention and battery is obviously easy than prior art, and with low cost, is of value to large-scale industrialization production.
Embodiment
Nonaqueous electrolytic solution of the present invention contains as electrolytical lithium salts and organic solvent, wherein, also contains alundum (Al in this electrolyte.
According to alundum (Al of the present invention is the nanoscale alundum (Al, and particle diameter can be the 1-500 nanometer.The particle diameter that reduces described alundum (Al can further improve its dispersiveness in electrolyte, so that the better effect of its performance, the particle diameter of described alundum (Al is preferably the 5-350 nanometer, and further under the preferable case, the particle diameter of described alundum (Al is the 10-50 nanometer.The content of described alundum (Al is low excessively, and effect is bad, and content is excessive then can to have a negative impact, and is benchmark with the total amount of electrolyte, and the content of described alundum (Al is 0.1-20 weight %, is preferably 0.1-10 weight %.Described nano level alundum (Al can be commercially available.
Of the present invention is the lithium salts that conventional lithium ion battery uses as electrolytical lithium salts.For example, can be LiPF6, LiAsF6, LiClO
4, LiBF
4, LiCF
3CO
2, Li (CF
3CO
2)
2N, LiCF
3SO
3, Li (CF
3SO
2)
3And Li (CF
3SO
2)
2Among the N one or more.The concentration of lithium salts can be the 0.5-2.0 mol in the general electrolyte, is preferably the 0.5-1.5 mol.
Organic solvent among the present invention is conventionally known to one of skill in the art.For example, can be dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, dipropyl carbonate, ethylene carbonate, propene carbonate, butylene, 1, in 3-dioxolanes, oxolane, 2-methyltetrahydrofuran and the gamma-butyrolacton one or more are preferably the mixed solvent of diethyl carbonate, methyl ethyl carbonate and ethylene carbonate.
The preparation method of electrolyte of the present invention comprises lithium salts, nanoscale alundum (Al and organic solvent mixed and gets final product.Described mixing can be dissolved into organic solvent with described lithium salts earlier, adds described alundum (Al then, mixes, and also can be earlier described alundum (Al to be joined in the organic solvent, mixes, and is adding described lithium salts, and mixing gets final product.In order to improve the dispersiveness of alundum (Al in organic solvent, under the preferable case, described alundum (Al in joining the electrolyte that is dissolved with lithium salts after, under agitation soaked 1-24 hour.Described stirring can be used conventional solution agitating device, for example, and magnetic stirring apparatus etc.Total amount with electrolyte is a benchmark, and it is 0.1-20 weight % that the amount of described lithium salts, nanoscale alundum (Al and organic solvent makes the content of described alundum (Al, is preferably 0.1-10 weight %.It can be the 0.5-2.0 mol that the amount of described lithium salts, nanoscale alundum (Al and organic solvent makes the concentration of described lithium salts, is preferably the 0.5-1.5 mol.The particle diameter of alundum (Al of the present invention can be the 1-500 nanometer.The particle diameter that reduces described alundum (Al can further improve its dispersiveness in electrolyte, so that the better effect of its performance, the particle diameter of described alundum (Al is preferably the 5-350 nanometer, and further under the preferable case, the particle diameter of described alundum (Al is the 10-50 nanometer.
Under the preferable case, described alundum (Al is with before electrolyte mixes, and 120-180 ℃ of baking 5-24 hour down, the water content that makes described alundum (Al is below 30ppm in advance.In order fully to remove the moisture of the minute quantity in the alundum (Al efficiently, described baking is preferably carried out in vacuum drying oven, and it is less than atmospheric pressure that the vacuum of described vacuum drying oven is pressed.
Lithium rechargeable battery of the present invention comprises electrode group and electrolyte, and described electrode group and electrolyte are sealed in the battery case, and described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole.
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 or 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, the conductive agent that generally includes positive active material, adhesive and optionally contain.
Described positive active material can be the positive active material of the embedded removal lithium embedded ion of this area routine, one or several in the preferred following material: Li
xM
yMn
2-yO
4, wherein, 0.9≤x≤1.2,0≤y≤1.0, M is a kind of in the elements such as lithium, boron, magnesium, aluminium, iron, cobalt, nickel, copper, gallium, yttrium, fluorine, iodine, sulphur; Li
xNi
yCo
1-yO
2, wherein, 0.9≤x≤1.1,0≤y≤1.0; Li
aNi
xCo
yMn
zO
2, wherein, 0≤a≤1.2, x+y+z=1,0≤x≤0.5,0≤y≤0.5,0≤z≤0.5.
Described adhesive can adopt the conventional all types of adhesives that are used to prepare lithium ion secondary battery positive electrode that use in the prior art, for example, can be in polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), butadiene-styrene rubber (SBR) and butadiene-styrene rubber (SBR) latex one or more.Weight with the positive active material in the positive electrode is benchmark, and the content of described adhesive is 2-10 weight %, is preferably 2-8 weight %.
Described conductive agent can be the anodal conductive agent of this area routine, at least a such as in acetylene black, conductive carbon black and the electrically conductive graphite.Conductive agent in second coating can be selected from one or more in the conductive agent that described positive electrode coating limited.Weight with the positive active material in the positive electrode is benchmark, and the content of conductive agent described in the positive electrode coating is 0-20 weight %, is preferably 2-15 weight %.
The negative pole of lithium rechargeable battery of the present invention is conventionally known to one of skill in the art.In general, described negative pole comprises collector body and coating and/or is filled in negative material on the conducting base.Described collector body is conventionally known to one of skill in the art, for example can be selected from aluminium foil, Copper Foil, nickel plated steel strip or Punching steel strip.Described negative active core-shell material is conventionally known to one of skill in the art, and it comprises negative electrode active material, adhesive and the conductive agent that optionally contains.
Described negative electrode active material is not particularly limited, can be the negative electrode active material of the embedded removal lithium embedded of this area routine, such as in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy one or more, preferred electrographite.
The adhesive of described negative pole comprises one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), the butadiene-styrene rubber (SBR).Weight with described negative electrode active material is benchmark, and the content of described adhesive is 0.1-10 weight %, is preferably 0.5-5 weight %.
The conductive agent of described negative pole is not particularly limited, and can be the cathode conductive agent of this area routine, for example, and can acetylene black, in conductive carbon black and the electrically conductive graphite one or more.Weight with negative electrode active material is benchmark, and the content of described conductive agent is 0-15 weight %, is preferably 2-10 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, be benchmark with the weight of negative electrode active material, the content of described solvent is 30-80 weight %, is preferably 35-60 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 lithium rechargeable battery provided by the invention comprises positive pole and the negative pole for preparing this battery, and positive pole, negative pole and the barrier film between positive pole and negative pole are prepared into pole piece, then pole piece is placed battery case, inject electrolyte, the sealed cell shell.
The preparation method of described positive pole can adopt conventional preparation method.For example,, apply and/or be filled on the described collector body positive active material, conductive agent and adhesive and solvent, drying, pressing mold or pressing mold not can obtain described positive pole.
The preparation method of described negative pole can adopt conventional preparation method.For example,, apply and/or be filled on the described collector negative electrode active material, conductive agent and adhesive and solvent, drying, pressing mold or pressing mold not can obtain described negative pole.
The preparation method of lithium rechargeable battery of the present invention is except described electrolyte uses nonaqueous electrolytic solution provided by the invention, and other step is conventionally known to one of skill in the art.The preparation method of lithium rechargeable battery provided by the invention is included between described positive pole for preparing and the negative pole membrane layer is set, constitute the electrode group, this electrode group is contained in the battery case, injects electrolyte, then the battery case sealing can be made lithium rechargeable battery.
Below by embodiment the present invention is described in more detail.
Embodiment 1
Present embodiment is used to that nonaqueous electrolytic solution provided by the invention, nonaqueous electrolytic solution are described, contains the lithium rechargeable battery of this electrolyte and their preparation method.
The preparation of electrolyte: 100 milliliters of ethylene carbonates, 100 milliliters of diethyl carbonates and 100 milliliters of methyl ethyl carbonates are mixed, add the LiPF6 of 45.6 grams as electrolyte lithium salt, stir, obtain the mixed solution that the electrolyte lithium salinity is 1.0 mol, add 1.13 gram alundum (Al (Dalian Luming Nanometer Material Co., Ltd. then, model LM2-N290, particle diameter is the 10-50 nanometer), total amount with electrolyte is a benchmark, the content of described alundum (Al is 0.3 weight %, stir, promptly get electrolyte.
Anodal preparation: with 90 gram polyvinylidene fluoride (Atuofeina Corp, 761#PVDF) be dissolved in 1350 gram N-N-methyl-2-2-pyrrolidone N-(NMP) solvents and make binder solution, then 2895 gram LiCoO2 (FMC Corp.'s production) are joined in the above-mentioned solution, fully mix and make anode sizing agent, this anode sizing agent is coated on the aluminium foil equably, makes long 70 millimeters, wide 19 millimeters, thick 125 microns positive pole through 125 ℃ of oven dry 1 hour, roll-in, cut-parts.The amount that applies makes every positive pole contain 6.2 gram LiCoO2.
The preparation of negative pole: (Jiangmen quantum Gao Ke company produces with 30 gram CMC CMC, 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 binder solution, with 1395 gram graphite (SODIFF company commodity, the trade mark is DAG84) join in this binder solution, mix and make the graphite cathode slurry, this cathode size is coated on the Copper Foil equably, through 125 ℃ of oven dry 1 hour, roll-in, cut-parts make long 70 millimeters, wide 19 millimeters, thick 125 microns negative pole.The amount that applies makes every negative pole contain 3.1 gram graphite.
The preparation of battery: the pole piece that the polypropylene screen of above-mentioned positive and negative plate and 20 micron thickness is wound into a rectangular lithium ion battery, pack in the battery case and weld, subsequently above-mentioned electrolyte is injected in the battery case, LP 053450A type lithium rechargeable battery A1 is made in sealing.
Comparative Examples 1
Method according to embodiment 1 prepares lithium rechargeable battery, and different is in the preparation of electrolyte, not add described alundum (Al.Obtain lithium ion battery D1 at last.
Embodiment 2
Method according to embodiment 1 prepares lithium rechargeable battery, different is, in the preparation of electrolyte, described alundum (Al (Dalian Luming Nanometer Material Co., Ltd., model LM2-N290, particle diameter is the 10-50 nanometer) consumption be 5.73 grams, be benchmark with the total amount of electrolyte, the content of described alundum (Al is 1.5 weight %.Described alundum (Al is before joining electrolyte, and baking 10 hours in the vacuum drying chamber of 130 handkerchiefs that 150 ℃, vacuum pressure are in advance, and then this alundum (Al joined electrolyte was stirred 5 hours described electrolyte under magnetic stirrer.Obtain lithium ion battery A2 at last.
Embodiment 3
Method according to embodiment 1 prepares lithium rechargeable battery, different is, in the preparation of electrolyte, described alundum (Al (Dalian Luming Nanometer Material Co., Ltd., model LM2-N290, particle diameter is the 50-200 nanometer) consumption be 11.64 grams, be benchmark with the total amount of electrolyte, the content of described alundum (Al is 3.0 weight %.After described alundum (Al joins electrolyte, under magnetic stirrer, described electrolyte was stirred 10 hours.Obtain lithium ion battery A3 at last.
Embodiment 4
Method according to embodiment 1 prepares lithium rechargeable battery, different is, in the preparation of electrolyte, described alundum (Al (Dalian Luming Nanometer Material Co., Ltd., model LM2-N290, particle diameter is the 200-500 nanometer) consumption be 19.82 grams, be benchmark with the total amount of electrolyte, the content of described alundum (Al is 5.0 weight %.After described alundum (Al joins electrolyte, under magnetic stirrer, described electrolyte was stirred 15 hours.Obtain lithium ion battery A4 at last.
Embodiment 5
Method according to embodiment 1 prepares lithium rechargeable battery, different is, in the preparation of electrolyte, described alundum (Al (Dalian Luming Nanometer Material Co., Ltd., model LM2-N290, particle diameter is the 200-500 nanometer) consumption be 32.75 grams, be benchmark with the total amount of electrolyte, the content of described alundum (Al is 8.0 weight %.After described alundum (Al joins electrolyte, under magnetic stirrer, described electrolyte was stirred 15 hours.Obtain lithium ion battery A5 at last.
Embodiment 6
The performance of the battery A1 that the present embodiment explanation embodiment of the invention 1 makes.
(1) cycle performance test
The BS-9300R secondary cell device for detecting performance that uses Qingtian Industry Co., Ltd., Guangzhou to produce is tested battery A1, and test environment is 25 ℃, relative humidity 30%, and assay method is as follows:
After 1C constant voltage charge to 4.2 volt, 20 milliamperes of charging cut-off currents.After shelving 5 minutes, be discharged to 3.0 volts, measure the initial discharge capacity that obtains battery with 1C.Repetition lies prostrate with 1C constant voltage charge to 4.2; Be discharged to 3.0 volts charge and discharge process again with 1C, write down the discharge capacity after the circulation the 200th, 300,400 time, calculate the discharge capacitance after the circulation 200,300,400 times according to following formula then.The result is as shown in table 1.
Discharge capacitance=the n time circulation back discharge capacity/initial discharge capacity * 100%
(2) over-charge safety performance test
A, get the lithium ion battery A1 that embodiment 1 makes, carry out the appearance cleaning.
B, with universal instrument the output current in constant current constant voltage source is transferred to 1A, output voltage transfers to 6V, closes the power supply in constant current constant voltage source then.With the high temperature adhesive plaster with the thermocouple probe of thermometer be fixed on the battery side in the middle of the place, battery surface is evenly wrapped up the loose thick about 12 millimeters asbestos of one deck, and when parcel, asbestos is compacted to thick about 6.5 millimeters.With current discharge to 3 volt of battery, use wire connected battery, universal instrument and constant current constant voltage source then, and the battery that connects is put to safety cabinet with 1A.Open the power supply in constant current constant voltage source then, battery is overcharged, open the universal instrument test voltage and change.
Need the careful voltage of noting battery in c, the test process, when cell voltage reaches 5 volts, immediately the voltage in constant current constant voltage source is turned down, to guarantee that battery can carry out constant voltage and overcharge under 5 volts.
Anomalies such as whether temperature, voltage and current variation and the battery of observing battery in d, the whole process leakage, breach take place, is smoldered, blast, on fire, swell write down the maximum temperature of battery surface simultaneously, and the result is as shown in table 2.
E, treat that electric current drops to 0.05A.1. the battery surface temperature then needs to continue to keep 8 hours ability at safety cabinet and takes out also more than 80 ℃; 2. the battery surface temperature is more than 45 ℃, and constant always, then need continue to keep ability taking-up in 6 hours at safety cabinet.
The condition that f, termination overcharge test comprises: the battery surface temperature reaches more than 200 ℃; Battery explosion or on fire; Electric current drops to below 50 milliamperes when overcharging; Cell voltage reaches 5 volts, and the battery surface temperature is lower than 40 ℃.
The over-charging of battery is judged that when finishing to overcharge test, tested battery described anomaly such as leakage, breach do not take place, is smoldered, blast, on fire, swell etc., is considered as by the over-charging test, otherwise is considered as not passing through according to measurement result.The result is as shown in table 2.
(3) thickness measuring
Measure preceding cell thickness of the middle charging for the first time of above-mentioned performance test (1) and the cell thickness after the 400th circulation with vernier caliper respectively, be calculated as follows the variation of cell thickness.The result is as shown in table 2.
Cell thickness before cell thickness-charging after time circulation of varied in thickness (millimeter)=400th
(4) normal temperature discharge capacity test
Get totally 5 of above-mentioned battery A1, use BS-9300R secondary cell device for detecting performance to carry out the discharge capacity test.Test environment is 25 ℃, relative humidity 30%, and assay method is as follows:
With the 1C current charges to 4.2V, then with the 0.5C current discharge to 3.0V, the record gained 5 discharge capacity value, average as discharge capacity.The result is as shown in table 2.
(5) high-temperature storage performance test
Battery A1 is lied prostrate with 1C constant-current constant-voltage charging to 4.2, measure original depth L1, place battery 85 ± 2 ℃ to store 48 hours down afterwards, after storing expiration, measure the thickness L2 (85 ℃ storage after thickness) of battery, after shelving 1 hour under 23 ± 7 ℃, battery is discharged to 3.0 volts with 1C then, the residual capacity of record battery, and measure cell thickness L3.Again battery is full of electricity and shelves current discharge to 3.0 volt of using 1C after 5 minutes, circulate continuously three times, write down the capacity (promptly recovering capacity) of each circulation and the thickness L4 (promptly recovering thickness) that the 3rd circulation is full of electricity.According to the capacity restoration rate and the self-discharge rate of following formula counting cell, the result is as shown in table 3.
Store thickness increase=L2-L1
Recover thickness increase=L4-L3
Self-discharge rate (%)=(initial capacity-residual capacity)/initial capacity * 100%
Recovery capacity/initial capacity * 100% of capacity restoration rate (%)=the 3rd circulation
(6) X-ray diffraction test (XRD)
Battery after the 400th circulation in the performance test (1) is dissected in glove box, positive electrode is taken out, carry out the XRD test with X-ray powder diffraction instrument (Japanese company of science produces, and model is D/MAX2200PC).The interplanar distance d of parameter value the 003rd crystal face diffracted intensity I003, the 006th crystal face diffracted intensity I006 that test obtains according to XRD, the 104th crystal face diffracted intensity I104, the 101st crystal face diffracted intensity I101, the 102nd crystal face diffracted intensity I102, the 110th crystal face
110, the 003rd crystal face interplanar distance d
003, the 006th crystal face interplanar distance d
006And the interplanar distance d of the 009th crystal face
009, unit cell volume V, the crystal structure order I003/I104 of positive active material and six sides ordering property (I006+I102)/I101 in the calculating positive electrode.The result is as shown in table 4.Wherein, unit cell volume V calculates as follows:
a＝2×d
110
c＝3×d
003＝6×d
006＝9×d
009
Comparative Examples 2
The performance of the battery D1 that this Comparative Examples explanation Comparative Examples 1 makes.
Measure the various performances of the battery D1 that Comparative Examples 1 makes according to the method for example 6, the result is shown in table 1-4.
Example 7-10
Following embodiment illustrates the performance of the battery A2-A5 that embodiment of the invention 2-5 makes.
Measure the various performances of the battery A2-A5 that embodiment 2-5 makes according to the method for example 6, the result is shown in table 1-4.
Table 1
| The battery source | Embodiment 1 | Comparative Examples 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| The battery numbering | A1 | D1 | A2 | A3 | A4 | A5 |
| Discharge capacitance (%) (200 circulation backs) | 86.0 | 79.2 | 87.0 | 86.5 | 85.6 | 85.0 |
| Discharge capacitance (%) (300 circulation backs) | 82.1 | 70.5 | 83.5 | 83.2 | 81.5 | 80.2 |
| Discharge capacitance (%) (400 circulation backs) | 78.2 | 62.0 | 80.9 | 79.6 | 77.5 | 76.5 |
As can be seen from Table 1, the battery A1-A5 that embodiment 1-5 makes is after 400 circulations, and discharge capacitance is all more than 75%, and the battery D1 that Comparative Examples 1 makes only is 62.0%.Obviously want high.Therefore, the battery that makes of the present invention has excellent cycle performance.
Table 2
As can be seen from Table 2, the over-charge safety performance of the battery A1-A5 that makes of embodiment 1-5 is better than the battery D1 that Comparative Examples 1 makes.Simultaneously, battery A1-A5 is after 400 circulations, and varied in thickness is all below 1 millimeter, and D1 has reached 1.320 millimeters.The normal temperature discharge capacity of battery A1-A5 is also wanted a little higher than battery D1.
Table 3
| The battery source | The battery numbering | Store thickness and increase (millimeter) | Recover thickness and increase (millimeter) | Self-discharge rate (%) | Capacity restoration rate (%) |
| Embodiment 1 | A1 | 0.82 | 0.45 | 18.59 | 89.55 |
| Comparative Examples 1 | D1 | 1.73 | 1.15 | 30.65 | 79.26 |
| Embodiment 2 | A2 | 0.69 | 0.37 | 15.23 | 90.66 |
| Embodiment 3 | A3 | 0.70 | 0.69 | 20.04 | 87.28 |
| Embodiment 4 | A4 | 1.06 | 0.77 | 21.25 | 87.09 |
| Embodiment 5 | A5 | 1.09 | 0.84 | 22.54 | 85.65 |
As can be seen from Table 3, the self-discharge rate of the battery A1-A5 that embodiment 1-5 makes is all below 25%, and the capacity restoration rate is all more than 85%, and the self-discharge rate of the battery D1 that Comparative Examples 1 makes is up to 30.65%, and the capacity restoration rate only is 79.26%.Simultaneously, battery A1-A5 also all is better than battery D1 in increase of storage thickness and the increase of recovery thickness.Therefore, the battery that makes of the present invention has the good high-temperature storge quality.
Table 4
| The battery source | Embodiment 1 | Comparative Examples 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| The battery numbering | A1 | D1 | A2 | A3 | A4 | A5 |
| V | 98.1552 | 99.9900 | 98.0156 | 98.0621 | 98.060 | 98.005 |
| I003/I104 | 2.401 | 2.366 | 2.420 | 2.413 | 2.398 | 2.396 |
| (I006+I102)/I101 | 0.9520 | 0.9650 | 0.9502 | 0.9510 | 0.9523 | 0.9531 |
As can be seen from Table 4, the positive active material of the battery D1 that the unit cell volume V of the positive active material of the battery A1-A5 that embodiment 1-5 makes and six sides ordering property (I006+I102)/I101 all makes than Comparative Examples 1 is little, and crystal structure order I003/I104 is then big than battery D1.Therefore, the present invention has suppressed the distortion of crystal structure in charge and discharge process of positive active material by adding nano level alundum (Al, makes structure cell maintain original smaller volume, keeps the order and the six sides ordering property of crystal structure.
Claims (11)
1. nonaqueous electrolytic solution, this electrolyte contains as electrolytical lithium salts and organic solvent, it is characterized in that, also contain alundum (Al in this electrolyte, the particle diameter of described alundum (Al is the 1-500 nanometer, total amount with electrolyte is a benchmark, and the content of described alundum (Al is 0.1-20 weight %.
2. electrolyte according to claim 1 wherein, is benchmark with the total amount of electrolyte, and the content of described alundum (Al is 0.1-10 weight %; In the electrolyte, the concentration of described lithium salts is the 0.5-2.0 mol.
3. electrolyte according to claim 1, wherein, the particle diameter of described alundum (Al is the 5-350 nanometer.
4. electrolyte according to claim 1, wherein, described lithium salts is LiPF6, LiAsF6, LiClO
4, LiBF
4, LiCF
3CO
2, Li (CF
3CO
2)
2N, LiCF
3SO
3, Li (CF
3SO
2)
3And Li (CF
3SO
2)
2Among the N one or more; Described organic solvent is that described organic solvent is selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, dipropyl carbonate, ethylene carbonate, propene carbonate, butylene, 1, one or more in 3-dioxolanes, oxolane, 2-methyltetrahydrofuran and the gamma-butyrolacton.
5. the preparation method of the described electrolyte of claim 1, this method comprises lithium salts and organic solvent is mixed, obtain nonaqueous electrolytic solution, it is characterized in that, this method also is included in the described nonaqueous electrolytic solution and adds alundum (Al, mixes, and the particle diameter of described alundum (Al is the 1-500 nanometer, total amount with electrolyte is a benchmark, and the content of described alundum (Al is 0.1-20 weight %.
6. method according to claim 5 wherein, is a benchmark with the total amount of electrolyte, and the content of described alundum (Al is 0.1-15 weight %; In the electrolyte, the concentration of described lithium salts is the 0.5-2.0 mol.
7. method according to claim 5, wherein, the particle diameter of described alundum (Al is the 5-350 nanometer.
8. method according to claim 5 wherein, after described alundum (Al joins described electrolyte, was under agitation mixed 1-24 hour.
9. method according to claim 5, wherein, the water content of described alundum (Al is below 30ppm.
10. lithium rechargeable battery, comprise electrode group and electrolyte, described electrode group and electrolyte are sealed in the battery case, described electrolysis group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, it is characterized in that described electrolyte is any described electrolyte among the claim 1-4.
11. the preparation method of the described lithium rechargeable battery of claim 10, this method comprises positive pole and the negative pole for preparing this battery, and positive pole, negative pole and the barrier film between positive pole and negative pole are prepared into pole piece, then pole piece is placed battery case, inject electrolyte, the sealed cell shell is characterized in that, described electrolyte is any described electrolyte among the claim 1-4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102082291A (en) * | 2010-12-29 | 2011-06-01 | 东莞市杉杉电池材料有限公司 | Lithium ion battery electrolyte containing nanoparticles |
| WO2016110126A1 (en) * | 2015-01-06 | 2016-07-14 | 宁波南车新能源科技有限公司 | Super capacitor organic electrolyte containing inorganic nanoparticle |
| CN113725486A (en) * | 2021-08-30 | 2021-11-30 | 慈溪斯昂尼电池有限公司 | Flame-retardant explosion-proof solid battery with stable polymer and ceramic electrolyte components |
-
2006
- 2006-12-26 CN CNB2006101705908A patent/CN100568604C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102082291A (en) * | 2010-12-29 | 2011-06-01 | 东莞市杉杉电池材料有限公司 | Lithium ion battery electrolyte containing nanoparticles |
| WO2016110126A1 (en) * | 2015-01-06 | 2016-07-14 | 宁波南车新能源科技有限公司 | Super capacitor organic electrolyte containing inorganic nanoparticle |
| CN113725486A (en) * | 2021-08-30 | 2021-11-30 | 慈溪斯昂尼电池有限公司 | Flame-retardant explosion-proof solid battery with stable polymer and ceramic electrolyte components |
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