CN100466365C - High safety, high power lithium ion power battery - Google Patents
High safety, high power lithium ion power battery Download PDFInfo
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- CN100466365C CN100466365C CNB2006101306166A CN200610130616A CN100466365C CN 100466365 C CN100466365 C CN 100466365C CN B2006101306166 A CNB2006101306166 A CN B2006101306166A CN 200610130616 A CN200610130616 A CN 200610130616A CN 100466365 C CN100466365 C CN 100466365C
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- battery
- lithium
- ion
- power cell
- barrier film
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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
This invention relates to the lithium ion batteries with high security and high power for electric bicycles, which is composed of the first anode film, the first cathode film, the second anode film, the second cathode film, separator, electrolyte and battery shell, and the batteries have the laser welding seal. The electrolyte is made of LiPF6, organic solvents, sufficient additive cyclohexyl benzene and flame retardant additive three beta TCEP. The cover of battery is installed with the injecting holes and explosion-prevented films. The winding order from inside to outside of battery core is the first anode film, separator, the first cathode film, separator, the second anode films, separator, the second cathode film, separator.
Description
Technical field
The present invention relates to lithium rechargeable battery, relate in particular to the high security that is suitable for electric bicycle and uses, hyperdynamic lithium-ion-power cell.
Background technology
Because environmental protection and requirements of saving energy, the world today is more and more urgent to the requirement of the energy, therefore seeks high efficiency, and clean power source, is the inexorable trend of social development and scientific progress.The current electrokinetic cell that is using and developing mainly contains lead acid accumulator, nickel-cadmium cell, Ni-MH battery and lithium ion battery.Compare the specific energy height (120-150Wh/kg) of lithium ion battery, specific power (250-350W/kg) height, life-span long (500-1000 circulation) with other electrokinetic cell.The 3-4 that energy density has reached lead-acid battery doubly, 2 times of Ni-MH battery, the specific energy height, can reach 570Wh/kg in theory, be the ideal source of electric motor car, also is the electrokinetic cell that is hopeful to reach the electrokinetic cell technical performance index in mid-term that the USABC of United States advanced association formulates most.
Though lithium ion battery has certain advantage in alternative traditional storage battery aspect the electrical source of power of electric motor car, but lithium ion battery under abuse or misuse state (as heat, overcharge, mistake is put, short circuit, vibration, extruding etc.), can cause inside battery generation vigorous reaction, produce a large amount of heat, if heat has little time to scatter and disappear and accumulates at inside battery, leakage may appear in battery, smolder, can occur catching fire, exploding when serious, power consumption equipment and user of service are caused in various degree injury, thus serious obstruction the process that maximizes of lithium ion battery.
Used lithium-ion battery electrolytes is 1mol/L LiPF at present
6EMC:EC:DMC (mass ratio 1:1:1), battery is overcharging, and is easy to take place thermal runaway when overheated, causes battery explosion or burning, and use equipment and user of service are damaged.The most of takeup type structure that adopts of at present used lithium-ion-power cell, the positive/negative plate of battery has only a slice, is unfavorable for the making of high-rate battery discharge and battery.
Summary of the invention
The objective of the invention is to the shortcoming that exists at prior art, the production program of a kind of high safety, new type lithium ion electrokinetic cell that high-rate discharge ability is good is provided.
The hyperdynamic lithium-ion-power cell of high security of the present invention is made up of first positive plate, first negative plate, second positive plate, second negative plate, barrier film, electrolyte and battery case, and battery is that Laser Welding is sealed; It is characterized in that: described electrolyte is made up of lithium hexafluoro phosphate (LiPF6), organic solvent, overcharging additive cyclohexylbenzene and flame-retardant additive three β one chloroethyl phosphate (TCEP); The cover plate of described battery case is provided with liquid injection hole, burst disk; The winding order of battery is respectively first positive plate, barrier film, first negative plate, barrier film, second positive plate, barrier film, second negative plate, barrier film from inside to outside.
Described organic solvent is that vinyl carbonate (EC), dimethyl carbonate (DMC), ethyl-methyl carbonic ester (EMC) are made into according to mass ratio 1:1:1; Lithium hexafluoro phosphate (LiPF
6) content be 1mol/L; Overcharging additive is that the mass content of cyclohexylbenzene is 5-7%, and optimum content is 5%; Flame-retardant additive is that the mass content of three β, one chloroethyl phosphate (TCEP) is 5-7%, and optimum content is 5%.
Described first positive pole and second positive pole are with active material LiMn
2O
4, conductive carbon black, PVDF be according to percentage by weight 85-88%, 7-9%, 5-6% proportioning, solvent is the N-methyl pyrrolidone, is uniformly coated on the metal aluminum foil two sides to make positive active material LiMn
2O
4The single face surface density is 17 ± 0.5mg/cm
2Described first negative pole and second negative pole are according to percentage by weight 90%, 3%, 7% proportioning with active material graphite, sodium carboxymethylcellulose, polystyrene fourth rubber, solvent is a water, be uniformly coated on the metal copper foil two sides and make, active material single face surface density is 8 ± 0.5mg mg/cm
2
Described cover plate wall thickness is 0.5 ± 0.03mm, and through being 1.4mm, burst disk is that the thin impression of copper forms in the liquid injection port.
The present invention has good overcharging resisting performance, good thermal stability and good dynamic property compared to existing technology.
Hereinafter, the present invention will carry out more detailed description by embodiment.But embodiment is used for understanding the present invention, and the present invention is not limited to following embodiment.
Embodiment
Embodiment 1
The preparation of anode pole piece: positive active material is LiMn
2O
4, active material, conductive carbon black, polytetrafluoroethylene be dissolved in the organic solvent N-methyl pyrrolidone (NMP) according to the ratio of 88:7:5 make slurry, with slurry coating in the aluminium foil two sides, anodal single face coated side density 17 ± 0.5mg/cm
2, after 120-130 ℃ of following drying, roll, cutting makes anode pole piece.
The first positive plate size: 1000 * 78 (units: mm)
The second positive plate size: 1050 * 78 (units: mm)
The preparation of cathode pole piece: negative electrode active material is a graphite, with graphite, sodium carboxymethylcellulose (CMC) polystyrene fourth rubber (SBR) by the 90:3:7 proportioning slurry of making soluble in water, with slurry coating in the Copper Foil two sides, negative pole single face coated side density 8 ± 0.5mg/cm
2, after 80-100 ℃ of vacuumize, cathode pole piece is made in roll-in, cutting.
The first negative plate size: 1020 * 78 (units: mm)
The second negative plate size: 1110 * 80 (units: mm)
The configuration of electrolyte: conventional lithium-ion battery electrolytes, cyclohexylbenzene (CHB) are according to the used electrolyte of 91-96:4-9 (mass ratio) deployment cost patent, and wherein Chang Gui lithium-ion battery electrolytes is the LiPF of 1mol/L
6Be dissolved in EMC:EC:DMC (mass ratio 1:1:1) solvent.
The assembling of battery: align in proper order according to first positive plate, barrier film, first negative plate, barrier film, second positive plate, barrier film, second negative plate, barrier film from top to bottom and put well, be rolled into battery with the volume pin and (guarantee two anode ear alignment, two negative electrode lug alignment maintain a certain distance between the positive and negative lug.Battery is put into F shaped steel shell, and with the anode ear welding on the cover board, negative electrode lug is welded on the box hat, and Laser Welding is sealed.Battery 80 ℃ of bakings 24 hours, is injected the electrolyte of 20 ± 1g then by liquid injection hole, the good seal liquid injection hole changes into, partial volume obtains the finished product battery.
Form F type battery, battery constant current pressure limiting, constant voltage and current limiting charge and discharge cycles 3 thoughtful lotus full power states are with the 1C-10V experiment of overcharging, result such as table 1.
The overcharging resisting ability of table 1 F type lithium-ion-power cell
(discharge voltage range 4.2-2.75V)
| Battery | Blank | 4％CHB | 5％CHB | 7％CHB | 9％CHB |
| No. 1 battery | Obvious flame explodes | Blast | The volumetric expansion of not exploding | Battery leakage does not explode | The volumetric expansion of not exploding |
| No. 2 batteries | Obvious flame explodes | Blast | The volumetric expansion of not exploding | Not blast | The volumetric expansion of not exploding |
| Maximum temperature (℃) | 190 | 140 | 130 | 113 | 110 |
| The 100th circulation volume conservation rate | 94.40％ | 95.46％ | 94.86％ | 93.69％ | 92.98％ |
By table 1 as seen, add the lithium ion battery of 5-9%CHB in the electrolyte under the situation that 1C-10V overcharges, there is not blast on fire, mainly be because when over-charging of battery cyclohexylbenzene generation electric polymerization reaction during to 4.65-4.75V, generate the poly-cyclohexylbenzene of conductive polymer membrane, cover on the anodal and close anodal barrier film, increase the internal resistance of cell, reduce electric current, the cyclohexylbenzene electropolymerization generates H simultaneously
2, activate explosion-proof valve, make it to open venting, prevented battery explosion.It can also be seen that increase simultaneously along with cyclohexylbenzene concentration, the capacity attenuation aggravation of battery, so the concentration of cyclohexylbenzene preferably is controlled between the 5-7%.
Embodiment 2
According to the identical program of embodiment 1, conventional lithium-ion battery electrolytes, three β, one chloroethyl phosphate (TCEP) are according to the used electrolyte of 90-96:4-10 (mass ratio) deployment cost patent, form F type battery, battery constant current pressure limiting, constant voltage and current limiting charge and discharge cycles 3 thoughtful lotus full power states, heat 30min in 150 ℃ thermostatic drying chamber, it the results are shown in Table 2
The overcharging resisting ability of table 2 F type lithium ion battery
(discharge voltage range 4.2-2.75V)
| Battery | Blank | 4％TCEP | 5％TCEP | 7％TCEP | 10％TCEP |
| No. 1 battery | Blast | Blast | Not blast | Not blast | Not blast |
| No. 2 batteries | Blast | Blast | Not blast | Not blast | Not blast |
| Maximum temperature (℃) | 160 | 168 | 150 | 145 | 145-150 |
| The 100th capability retention | 94.40％ | 93.02％ | 91.51％ | 88.42％ | 86.41％ |
By table 2 as seen, when the content of TCEP less than 5% the time, can not play high temperature protection effect fully to battery, have only the amount of additive to surpass 5% after, could stop the blast of lithium ion battery.This is to absorb the chain reaction that hydroperoxyl radical has stoped electrolyte because TCEP separated in the high temperature time-division, and the chloroethanes that generates simultaneously gasification absorbs heat.As can be seen along with the increase of additive amount, loop attenuation is serious, so the consumption of TCEP is preferably between 5-7% simultaneously.
Embodiment 3
According to the identical program of embodiment 1, just 1mol/L LiPF
6EMC:EC:DMC electrolyte in add the cyclohexylbenzene and the TCEP composition research electrolyte of different proportion simultaneously.Form F type battery, battery constant current pressure limiting, 3 weeks of constant voltage and current limiting charge and discharge cycles are put the lotus full power state, overcharge or heat 30min in 150 ℃ thermostatic drying chamber, table 3 between its result with 1C-10V
The overcharging resisting ability and the heat-resisting ability of table 3 F type lithium ion battery
(discharge voltage range 4.2-2.75V)
| Battery | Blank | 4％CHB+4％ TCEP | 5％CHB+5％ TCEP | 6％CHB+10％ TCEP |
| Overcharge experiment | Blast | Blast | Not blast | Not blast |
| The heating experiment | Blast | Blast | Not blast | Not blast |
| The 100th capability retention | 94.40％ | 90.21％ | 88.3％ | 83.61 |
By example 1-3 as can be seen in the electrolyte additive 5%CHB and 5%TCEP promptly can prevent the fail safe of lithium ion battery when overcharging with high temperature, be unlikely to again the comprehensive electrochemical properties of battery is caused especially big influence, be proper adding proportion.
Embodiment 4
According to the identical program of embodiment 1, the just anodal LiMn that presses
2O
4: the ratio batch mixing of PVDF: electrically conductive graphite=90:5:5.1mol/L LiPF
6EMC:EC:DMC electrolyte in add 5% cyclohexylbenzene and 5%TCEP composition research electrolyte.Form F type battery, battery constant current pressure limiting, constant voltage and current limiting charge and discharge cycles test data such as table 4, the charge-discharge performance scope is 4.2-2.75V unit: Ah.The security test of battery is with example 1, example 2.
The discharge performance of table 4 lithium-ion-power cell under different discharge current densities
(discharge voltage range 4.2-2.75V)
Because requirement easy to use, it is good that the rapid charge characteristic of electrokinetic cell is wanted, and the big capacity secondary battery that is used for electric bicycle is under the situation of vehicle launch, acceleration and climbing, also require as can heavy-current discharge so that enough power to be provided, so heavy-current discharge performance is one of Essential Performance Requirements of electrokinetic cell always.The heat dispersion of the bipolar ear batteries in parallel connection of above-mentioned design is better than the heat dispersion of monopole ear, thereby helps heavy-current discharge.
Embodiment 5
According to the identical program of embodiment 3, just 1mol/L LiPF
6EMC:EC:DMC electrolyte in add 5% cyclohexylbenzene and 5%TCEP composition research electrolyte.Form F type battery, battery constant current pressure limiting, constant voltage and current limiting charge and discharge cycles test data such as table 5, the charge-discharge performance scope is 4.2-2.75V unit: Ah.The security test of battery is with example 1, example 2.
The discharge performance of table 5 lithium-ion-power cell under different discharge current densities
(discharge voltage range 4.2-2.75V)
Embodiment 5 explanations are after conductive agent content is increased to 7%, and large current discharging capability obviously improves, and the multiplying power cycle performance strengthens, and can satisfy the power requirement of electric bicycle substantially.
Embodiment 6
According to the identical program of embodiment 5, the just anodal LiMn that presses
2O
4: the ratio batch mixing of PVDF: electrically conductive graphite=85:9:6.
The discharge performance of table 6 lithium-ion-power cell under different discharge current densities
(discharge voltage range 4.2-2.75V)
Example 6 explanations are after conductive agent content is increased to 9%, and the F type battery high rate performance of design improves, and the cyclical stability under the high magnification strengthens, but the discharge capacity of battery reduces simultaneously, mainly are because the increase of conductive agent content is equivalent to the active material minimizing.
As can be seen along with the increase of conductive agent content, the power performance of F type battery improves by embodiment 4-6, and large current discharging capability strengthens, but conductive agent content is too high, will cause the decay of battery capacity, so rational proportion should be LiMn
2O
4: PVDF: electrically conductive graphite=(85-88): (7-9): (5-6).
Claims (6)
1. a lithium-ion-power cell is made up of first positive plate, first negative plate, second positive plate, second negative plate, barrier film, electrolyte and battery case, and battery is that Laser Welding is sealed, and it is characterized in that: described electrolyte is by lithium hexafluoro phosphate (LiPF
6), organic solvent, overcharging additive cyclohexylbenzene and flame-retardant additive three β one chloroethyl phosphate (TCEP) form; Described organic solvent is that vinyl carbonate, dimethyl carbonate, ethyl-methyl carbonic ester are made into lithium hexafluoro phosphate (LiPF according to mass ratio 1:1:1
6) content be 1mol/L, the mass content of overcharging additive cyclohexylbenzene is 5-7%, the mass content of flame-retardant additive three β one chloroethyl phosphate (TCEP) is 5-7%; The cover plate of described battery case is provided with liquid injection hole, burst disk; The winding order of battery is respectively first positive plate, barrier film, first negative plate, barrier film, second positive plate, barrier film, second negative plate, barrier film from inside to outside.
2. according to the described lithium-ion-power cell of claim 1, it is characterized in that: the mass content of described overcharging additive cyclohexylbenzene is 5%; Flame-retardant additive is that the mass content of three β, one chloroethyl phosphate (TCEP) is 5%.
3. according to the described lithium-ion-power cell of claim 1, it is characterized in that described first, second positive plate is with active material LiMn
2O
4, conductive carbon black, PVDF be according to percentage by weight 85-88%, 7-9%, 5-6% proportioning, solvent is the N-methyl pyrrolidone, is uniformly coated on the metal aluminum foil two sides to make; Described first, second negative plate be with active material graphite, sodium carboxymethylcellulose, polystyrene fourth rubber according to percentage by weight 90%, 3%, 7% proportioning, solvent is a water, is uniformly coated on the metal copper foil two sides to make.
4. according to the described lithium-ion-power cell of claim 3, it is characterized in that: described positive active material LiMn
2O
4The single face surface density is 17 ± 0.5mg/cm
2
5. according to the described lithium-ion-power cell of claim 3, it is characterized in that: described negative electrode active material single face surface density is 8 ± 0.5mg/cm
2
6. according to any one described lithium-ion-power cell of claim 1 to 5, it is characterized in that: burst disk is that the Copper Foil impression forms.
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| CNB2006101306166A CN100466365C (en) | 2006-12-27 | 2006-12-27 | High safety, high power lithium ion power battery |
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| CNB2006101306166A CN100466365C (en) | 2006-12-27 | 2006-12-27 | High safety, high power lithium ion power battery |
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| CN100466365C true CN100466365C (en) | 2009-03-04 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101771167B (en) * | 2010-02-05 | 2013-09-25 | 九江天赐高新材料有限公司 | High-capacity lithium-ion electrolyte, battery and preparation method of battery |
| CN102751531B (en) * | 2011-12-30 | 2015-04-22 | 华明电源(深圳)有限公司 | Lithium ion secondary battery |
| CN102779977B (en) * | 2011-12-30 | 2015-06-03 | 华明电源(深圳)有限公司 | Polymer lithium ion battery and manufacturing method of positive plate of battery |
| CN102683746A (en) * | 2012-05-04 | 2012-09-19 | 百顺松涛（天津）动力电池科技发展有限公司 | Lithium battery electrolyte additive and electrolyte using same as well as battery |
| CN102780042B (en) * | 2012-08-01 | 2015-04-15 | 浙江努奥罗新能源科技有限公司 | Lithium-ion power battery pack for electric bicycle |
| CN108242556B (en) * | 2016-12-26 | 2020-01-17 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and secondary battery |
| CN111710908A (en) * | 2020-06-22 | 2020-09-25 | 中国电力科学研究院有限公司 | Direct-current power supply lithium ion battery and preparation method thereof |
| CN113514528A (en) * | 2021-03-10 | 2021-10-19 | 首钢集团有限公司 | Method for measuring compactness of hot-dip galvanized sheet inhibition layer |
| CN116111044A (en) * | 2023-04-11 | 2023-05-12 | 宁德新能源科技有限公司 | Positive electrode sheet, secondary battery, and electronic device |
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| US5580684A (en) * | 1994-07-07 | 1996-12-03 | Mitsui Petrochemical Industries, Ltd. | Non-aqueous electrolytic solutions and non-aqueous electrolyte cells comprising the same |
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