CN102412414A - Manufacturing method of power novel lithium ion battery capable of being charged safely under low temperature - Google Patents
Manufacturing method of power novel lithium ion battery capable of being charged safely under low temperature Download PDFInfo
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- CN102412414A CN102412414A CN2010102897013A CN201010289701A CN102412414A CN 102412414 A CN102412414 A CN 102412414A CN 2010102897013 A CN2010102897013 A CN 2010102897013A CN 201010289701 A CN201010289701 A CN 201010289701A CN 102412414 A CN102412414 A CN 102412414A
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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
Abstract
The invention provides a manufacturing method of a power novel lithium ion battery capable of being charged safely under low temperature. The manufacturing method comprises the following steps of: for a negative piece, adopting modified graphite as a negative active material, adopting a pore-forming technology in coating to lead the negative piece to have a porous structure; arranging the negative piece, a positive piece and a diaphragm into an electric core after being combined, injecting low-temperature electrolyte, sealing and intelligently forming, i.e., firstly precharging 60% electric quantity for the battery by 0.1C current, then carrying out ageing and standing treatment for 24-72h under the temperature of 40-60 DEG C, forming by 0.2C current and leading an SEI (solid electrolyte interface) film with a stable structure and less impedance to be formed on the surface of the negative piece, and obtaining the lithium ion battery. In the manufactured power novel lithium ion battery, the low-temperature charging performance is better, the polarization is low when in charging under low temperature and no precipitated lithium is formed on the surface of a negative electrode, so that the reduction of the safety performance of the battery due to aggregation of lithium dendrites is avoided.
Description
[technical field]
The present invention relates to use lithium and cobalt oxides LiCoO
2, lithium nickel oxide LiNiO
2, lithium-cobalt-nickel oxide LiCoNiO
2, lithium manganese oxide LiMn
2O
4,, nickel cobalt manganese lithium oxide Li
αNi
βCo
γMn
δO
2Or lithium iron phosphate LiFePO
4Deng one or more as positive active material; Modified graphite is as negative electrode active material; Low-temperature electrolytes is as electrolyte; Adopt the coating technique of pore-creating, column type or rectangular lithium ion battery that the processing mode of process coiling or lamination is prepared from change into the lithium ion battery that forms through intelligence again.
[background technology]
Nineteen ninety, Sony Corporation takes the lead in releasing with LiCoO in the laboratory
2Be the lithium rechargeable battery of positive electrode, and in beginning industrialization in 1991.Lithium rechargeable battery is fast-developing for over ten years, rely on its specific energy high, have extended cycle life, advantages such as self discharge is little, output voltage is high, green non-pollution, technical development speed is swift and violent.The product market share rate of climb is that any up to now chemical cell is incomparable, suddenly becomes the battery product of the strength of present World Battery Market public attention.According to statistics, the sales volume of global lithium ion battery has surpassed the summation of ni-mh, nickel-cadmium cell.
Along with the progress of society, the increasing of material wealth, living in of people improves constantly, and people's environmental consciousness is also strengthening day by day simultaneously.European Union begins the restriction nickel-cadmium cell in certain fields at present.Therefore, the battery of high power, long-life, pollution-free, low-cost, high reliability, high security becomes the product of some field active demand of the modern life.The supporting power supply that mainly comprises electric tool.
Be in first-chair nickel-cadmium cell on the electric tool market owing to exist pollution problem progressively to step down from the stage of history, the product that substitutes it at present mainly is a Ni-MH battery.People begin to develop power-type lithium ion battery now, prepare to substitute NI-G, Ni-MH battery.
But all there is following defective in present common power-type lithium ion battery:
1. charging temperature all requires more than 0 ℃, all exists battery impedance to increase in charging below 0 ℃, and negative terminal surface is analysed lithium, and battery is poor in the cycle life below 0 ℃.Limited the use of battery at cold district.
2. low temperature rechargeable battery polarizing voltage increases, and when using the charger charging, can find the lantern festival flicker, makes troubles to the user.
3. after improving cryogenic property, because the SEI membrane structure of negative terminal surface is stable inadequately, battery can on fire, blast when safety tests such as acupuncture, extruding.
[summary of the invention]
The present invention provides the manufacturing approach of the power new type lithium ion battery of safe charging under a kind of ability low temperature.The characteristics of this method are to adopt modified graphite as negative pole, shorten Li
+Embed the time of graphite, form Li dendrite in negative terminal surface when preventing to charge at low temperatures, improve the fail safe of battery; The anodal constitutionally stable positive electrode of good conductivity that adopts is convenient to Li when low temperature charges
+Deviate from, reduce the polarization of battery; Electrolyte adopts the good electrolyte of cryogenic property; It is main because the electrolyte of lithium ion battery is organic electrolyte; Electric conductivity is relatively poor at low temperatures, and the present invention adopts the PC, 1 that fusing point is low, relative dielectric constant is high, and 2-BC, gamma-butyrolacton, ethyl acetate etc. are as solvent; VC, PS etc. improve the cryogenic property of electrolyte as additive; With the centre of lug location arrangements at pole piece, material uses red copper to replace traditional nickel lug, reduces the polarization resistance of battery, improves the low-temperature safety charging performance of battery.The problem division of approach that passes through and solution is following:
1. the power new type lithium ion battery of the hypopolarization when adopting modified graphite to be prepared into the low temperature charging as negative material.Because modified graphite is handled through modification, its interlamellar spacing shortens, and graphite surface makes Li with the conductive agent full contact
+When charging, embed the graphite layers reduced distances, reduce polarization, can increase the service life.Because the conductive capability of electrolyte under low temperature condition reduces, and battery the 1C charging current is bigger at low temperatures, make Li in the positive pole
+The time can not get into the interlayer of graphite cathode in charging at once, cause at the graphite cathode surface deposition, form Li dendrite, in a single day Li dendrite grows up, and diaphragm easily causes internal short-circuit of battery and causes security incident.Use modified graphite, use profile to be lepidiod modified graphite, the interlamellar spacing of graphite shortens, and has improved the electric conductivity of graphite cathode, makes Li
+When low temperature charges, be easy to arrive graphite layers, reduce the probability that forms Li dendrite in negative terminal surface, improve the security performance of battery, reduce polarization simultaneously, improve the cycle performance of battery.
2. adopt the electrolyte of the power new type lithium ion battery of low temperature resistant, the hypopolarization when high security electrolyte charges as low temperature.Adopt the PC, 1 that fusing point is low, relative dielectric constant is high, 2-BC, gamma-butyrolacton, ethyl acetate etc. are as solvent, and VC, PS etc. improve the cryogenic property of electrolyte as additive.
3. preferred positive electrode improves battery structure, can be with the 1C current charges under-10 ℃ of conditions, and charging capacity reaches under 80%, 0 ℃ of condition of rated capacity with 1C current charges, polarizing voltage≤100mV.
4. optimize the battery pole piece manufacture craft, on fire, blast can not take place after making battery be full of electricity under puncture, extruding condition.
5. adopt intelligence to change into; Earlier with the electric weight of battery with 0.1C pre-charge 60%; Under 40-60 ℃ of temperature, shelve 24-72h again and handle, change into the 0.2C electric current again, make negative terminal surface form Stability Analysis of Structures, the little SEI film of impedance through overaging; Thereby the lithium ion battery of processing can have the consistency of excellent cycle performance and performance simultaneously again on the basis with good low-temperature charging performance.
The power new type lithium ion battery production Technology of safe charging comprises under the ability low temperature provided by the present invention:
1. the preparation of negative electrode:
As negative electrode active material, electrically conductive graphite is as additive with modified graphite, and PVdF makees solvent as binding agent with NMP, and the high-speed stirred of process certain hour makes cathode size, is coated on the two sides of Copper Foil equably, makes negative electrode after the oven dry.
2. the preparation of positive electrode:
(1) slurrying: the composition of positive electrode slurry (wt%) is: dedicated solvent 20-60, binding agent (1.1-difluoroethylene etc.) 2-12, electric conducting material (carbon black, graphite etc.) are made additive 1-8, pulverous positive active material (lithium and cobalt oxides LiCoO
2, lithium nickel oxide LiNiO
2, lithium-cobalt-nickel oxide LiCoNiO
2, lithium manganese oxide LiMn
2O
4,, nickel cobalt manganese lithium oxide Li
αNi
βCo
γMn
δO
2Or lithium iron phosphate LiFePO
4Deng one or more.)30-50。Dedicated solvent, binding agent and conductive additive are mixed with pulverous positive active material respectively, and, vacuum even through high-speed stirred makes.
(2) coating: anode sizing agent is coated on the two sides of aluminium foil equably, makes positive electrode after the oven dry.
3. coiling (lamination) assembling: the mutual corresponding winding shaping of the positive pole that will design in advance, barrier film and negative pole, or assembling becomes battery in the electric housing of packing into after the assembled in forms with lamination.Battery case can be columniform, also can be square; Case material matter is that aluminium, stainless steel, nickel-plated steel, aluminum-plastic composite membrane etc. are not limit.
4. the preparation of low-temperature electrolyte: PC, 1,2-BC, gamma-butyrolacton, ethyl acetate etc. are as solvent, and VC, PS etc. is mixed with low-temperature electrolyte as additive.The concentration of additive such as VC, PS in organic solvent is every liter of 2-10 gram.
5. fluid injection:, introduce in the battery the quantity of the low-temperature electrolyte for preparing in advance by the battery product design.Then, seal with sealing machine or seal the 4th edge of Soft Roll shell with heat sealing machine.
6. change into and place:, under 40-60 ℃ of temperature, shelve 24-72h again and handle the electric weight of finished product battery with special-purpose battery charging and discharging equipment, change into the 0.2C electric current again through overaging with 0.1C pre-charge 60%; Form the protection mould at negative electrode surface; After placing several weeks then, remake discharge test, each battery is all detected; Filter out qualified finished product battery, wait to dispatch from the factory.
According to product design that this method provided and technology produce next life be equipped with can low temperature under the power new type lithium ion battery of safe charging will reach following technique effect:
1. product low temperature charging performance improves
With the 1C current charges, charging capacity can reach 80% of rated capacity to the power new type lithium ion battery of safe charging under-10 ℃ of conditions under the ability low temperature of the present invention; Under 0 ℃ of condition with 1C current charges, polarizing voltage≤100mV.
With the 1C current charges, charging capacity is merely 60% of rated capacity to common power-type lithium ion battery under-10 ℃ of conditions; With the 1C current charges, polarizing voltage reaches more than the 300mV under 0 ℃ of condition.
2. the safety of products performance improves
On fire, blast can not take place after being full of electricity in the power new type lithium ion battery of safe charging under the ability low temperature of the present invention under puncture, extruding condition.
3. the cycle performance under the low temperature environment improves
Because power new type lithium ion battery charging capacity under low temperature environment of safe charging is high under the ability low temperature of the present invention, voltage polarizing is little, and the probability that forms Li dendrite in negative terminal surface obviously reduces, thereby has improved the cycle life of battery under low temperature environment greatly.The phenomenon of lamp flicker can not appear in the user when using the charger charging.
4. the properties of product consistency increases
In production technology of the present invention, adopted intelligence to change into; Battery is being carried out the certain electric weight of little pre-charge electricity; Pass through burin-in process more at a certain temperature; In the process that changes into little electric current again, can form even structure, stable, the little SEI film of impedance in negative terminal surface, thereby the battery performance consistency is increased.
[embodiment]
Embodiment one:
The compound method of low-temperature electrolyte:
Electrolytic salt is selected lithium hexafluoro phosphate LiPF for use
6, adopt the PC, 1 that fusing point is low, relative dielectric constant is high, 2-BC, gamma-butyrolacton, ethyl acetate etc. are as solvent, VC, etc. as additive, subsequent use after evenly mixing.
Table 1 different electrolytes compound method test comparison data: (being made into lithium iron phosphate 18650-1100 power-type lithium ion battery tests)
Table 1
| Sequence number | 1# | 2# | 3# | 4# | Common power-type lithium ion battery |
| PC | 1 | 1 | 1 | 1 | / |
| 1，2-BC | 1 | 1 | 1 | 1 | / |
| Gamma-butyrolacton | 1 | 0 | 1 | 0 | / |
| Ethyl acetate | 0 | 1 | 0 | 1 | / |
| VC (grams per liter) | 4 | 0 | 2 | 3 | / |
| PS (grams per liter) | 0 | 4 | 2 | 3 | / |
| -10 ℃ of 1C current charges capacity/% | 71 | 72 | 75 | 82 | 61 |
| 0 ℃ of 10C current charges polarizing voltage/mV | 189 | 190 | 152 | 95 | 317 |
Embodiment two:
The manufacturing approach of the anodal core of lithium ion cell of takeup type lithium iron phosphate:
The manufacturing approach of electrode film:
With positive electrode lithium iron phosphate LiFePO
4, conductive agent Super " P ", bonding agent PVDF, solvent NMP 100: 2.5: 3.5 by weight proportion: 47 synthetic slurries are coated on the 0.02mm thick aluminum foil.It is the 56mm elongated that positive electrode band cutting is become width: the aluminium foil of not filming is left in the pole piece appropriate location, and its surface will be at the subsequent handling mid point aluminum lead of burn-oning.
The manufacturing approach of negative electrode plate:
With negative material modified graphite, conductive agent, bonding agent, solvent 100: 7: 6 by weight proportion: 52 synthetic slurries were coated on the thick Copper Foil of 0.01mm.Negative electrode band cutting is become wide 57mm elongated: the Copper Foil of not filming is left in the pole piece appropriate location, and its surface will be at the subsequent handling mid point nickel down-lead of burn-oning.
Positive and negative electrode band and barrier film are sequenced by positive electrode/barrier film/negative electrode/barrier film in proper order, be placed on the up-coiler, be wound into 18650 battery.The positive and negative electrode lead-in wire grows battery 15mm, parallel interval 10mm.Battery is packed in the nickel plating box hat, and fluid injection is treated in the some end, slot rolling, baking.
On special equipment, carry out a cap seal mouth behind 4.5 milliliters of injections of 4# electrolyte battery among the embodiment one that under dry environment, will prepare in advance.
Shelve after sealing and use special-purpose battery charging and discharging equipment after 12-24 hour, under 40-60 ℃ of temperature, shelve 24-72h again and handle, change into the 0.2C electric current again and accomplish whole preparation technology's operations through overaging to the electric weight of battery with 0.1C pre-charge 60%.
Embodiment three:
The manufacturing approach of stacked lithium manganese oxide, nickel cobalt manganese lithium oxide blended anode core of lithium ion cell:
The manufacturing approach of electrode film:
With positive electrode Mn oxide LiMn
2O
4,, nickel cobalt manganese lithium oxide Li
αNi
βCo
γMn
δO
2LiFePO
4, conductive agent Super " P ", bonding agent PVDF, solvent NMP 20: 80: 2.5 by weight proportion: 3.5: 47 synthetic slurries are coated on the 0.02mm thick aluminum foil.Positive electrode band cutting is become chopper type: the operator area is 50 * 70mm
2Size, hilt area are 5 * 7mm
2Size, hilt partly are the aluminium foils of not filming, and its surface will be at the subsequent handling mid point aluminum lead of burn-oning.
The manufacturing approach of negative electrode plate:
With negative material modified graphite, conductive agent, bonding agent, solvent 100: 7: 6 by weight proportion: 52 synthetic slurries were coated on the thick Copper Foil of 0.01mm.Negative electrode band cutting is become chopper type: the operator area is 51.5 * 71.5mm
2Size, hilt area are 5 * 7mm
2Size, hilt partly are the Copper Foils of not filming, and its surface will be at the subsequent handling mid point nickel down-lead of burn-oning.
The manufacturing approach of stacked battery core:
With positive, negative electrode plate and compound film sheet press positive electrode/composite membrane/negative electrode/composite membrane/... the order of/electrode film sequences, and has 6 negative electrode plates, 7 double-side membrane electrode films and 2 single face film negative electrode plates, constitutes 2.5 * 50 * 70mm
3Battery.The hilt aluminium foil of 7 electrode films pools together and is welded on the aluminum lead.6 double-side membrane negative electrode plates and 2 single face film negative electrode plate hilt Copper Foils pool together and are welded on the nickel down-lead, and the positive and negative electrode lead-in wire grows battery 15mm, parallel interval 20mm.Battery is packed in the aluminum-plastic composite membrane outer packaging bag, use hot press to seal and edge sealing, stay a mouth to be used for fluid injection.
On special equipment, carry out the hot sealing liquid injection port behind 3.0 milliliters of injections of 4# electrolyte battery among the embodiment one that under dry environment, will prepare in advance.
Changing into and exhaust mouth-sealing method again of battery:
Use special-purpose battery charging and discharging equipment earlier with the electric weight of battery, under 40-60 ℃ of temperature, shelve 24-72h again and handle, change into the 0.2C electric current again through overaging with 0.1C pre-charge 60%.。Emit the little of gas that in formation process, produces then, seal at last and accomplish whole preparation technology's operations.
Battery and common motive-power battery test comparison data that table 2 embodiment two, three makes:
Table 2
| Test event | Embodiment two | Embodiment three | Common motive-power battery |
| -10 ℃ of 1C current charges capacity/% | 82 | 81 | 61 |
| 0 ℃ of 10C current charges polarizing voltage/mV | 95 | 97 | 317 |
| 1C circulation (capacity attenuation to 80%)/inferior | 554 | 561 | 405 |
| Acupuncture | Not on fire, do not explode | Not on fire, do not explode | On fire |
| Extruding | Not on fire, do not explode | Not on fire, do not explode | Smolder |
Annotate: data are testing mean in the above table.
Claims (7)
1. the power new type lithium ion battery of safe charging under the ability low temperature is characterized in that this battery comprises positive pole, negative pole, barrier film and low-temperature electrolytes.
2. the power new type lithium ion battery of safe charging is characterized in that positive active material is lithium and cobalt oxides LiCoO2, lithium nickel oxide LiNiO under the ability low temperature as claimed in claim 1
2, lithium-cobalt-nickel oxide LiCoNiO
2, lithium manganese oxide LiMn
2O
4, nickel cobalt manganese lithium oxide Li
αNi
βCo
γMn
δO
2Or lithium iron phosphate LiFePO
4Deng one or more.
3. the power new type lithium ion battery of safe charging is characterized in that negative electrode active material is a modified graphite under the ability low temperature as claimed in claim 1, adopts boring technique during the negative pole coating.
4. the power new type lithium ion battery of safe charging under the ability low temperature as claimed in claim 1; Change into through intelligence when it is characterized in that preparing; With the electric weight of battery, under 40-60 ℃ of temperature, shelve 24-72h again and handle earlier, change into the 0.2C electric current again through overaging with 0.1C pre-charge 60%.
5. the power new type lithium ion battery of safe charging under the ability low temperature as claimed in claim 1, positive pole, barrier film, negative pole assemble through coiling or lamination mode when it is characterized in that the battery assembling.
6. the power new type lithium ion battery of safe charging under the ability low temperature as claimed in claim 1; It is characterized in that this battery can be with the 1C current charges under-10 ℃ of conditions; Charging capacity reaches under 80%, 0 ℃ of condition of rated capacity with 1C current charges, polarizing voltage≤100mV.
7. the power new type lithium ion battery of safe charging under the ability low temperature as claimed in claim 1 is characterized in that after this battery is full of electricity on fire, blast not taking place under puncture, extruding condition.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682313A (en) * | 2013-12-11 | 2014-03-26 | 高建军 | Preparation method of surface-coating anode material of lithium ion battery |
| CN104934636A (en) * | 2015-06-17 | 2015-09-23 | 宁德时代新能源科技有限公司 | Electrolyte and lithium ion battery containing same |
| CN107482253A (en) * | 2017-07-18 | 2017-12-15 | 东莞市迈科新能源有限公司 | A kind of low-temperature lithium ion battery |
| CN109888290A (en) * | 2019-03-19 | 2019-06-14 | 郑州中科新兴产业技术研究院 | A kind of high multiplying power lithium ion battery, ageing and chemical synthesizing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1614800A (en) * | 2003-11-04 | 2005-05-11 | 上海杉杉科技有限公司 | Preparing method for carbon negative material of lithium ion battery |
| CN101640285A (en) * | 2008-07-28 | 2010-02-03 | 上海比亚迪有限公司 | Formation method of lithium ion secondary battery |
-
2010
- 2010-09-25 CN CN2010102897013A patent/CN102412414A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1614800A (en) * | 2003-11-04 | 2005-05-11 | 上海杉杉科技有限公司 | Preparing method for carbon negative material of lithium ion battery |
| CN101640285A (en) * | 2008-07-28 | 2010-02-03 | 上海比亚迪有限公司 | Formation method of lithium ion secondary battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682313A (en) * | 2013-12-11 | 2014-03-26 | 高建军 | Preparation method of surface-coating anode material of lithium ion battery |
| CN104934636A (en) * | 2015-06-17 | 2015-09-23 | 宁德时代新能源科技有限公司 | Electrolyte and lithium ion battery containing same |
| CN107482253A (en) * | 2017-07-18 | 2017-12-15 | 东莞市迈科新能源有限公司 | A kind of low-temperature lithium ion battery |
| CN109888290A (en) * | 2019-03-19 | 2019-06-14 | 郑州中科新兴产业技术研究院 | A kind of high multiplying power lithium ion battery, ageing and chemical synthesizing method |
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Application publication date: 20120411 |