CN102709530A - Power lithium ion battery with over-charge and over-discharge protection function and preparation method thereof - Google Patents
Power lithium ion battery with over-charge and over-discharge protection function and preparation method thereof Download PDFInfo
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- CN102709530A CN102709530A CN2012101938462A CN201210193846A CN102709530A CN 102709530 A CN102709530 A CN 102709530A CN 2012101938462 A CN2012101938462 A CN 2012101938462A CN 201210193846 A CN201210193846 A CN 201210193846A CN 102709530 A CN102709530 A CN 102709530A
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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
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Abstract
The invention relates to a power lithium ion battery with an over-charge and over-discharge protection function and a preparation method thereof. The power lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and an outer package, wherein the positive electrode comprises 90-95wt% of modified positive active substance and the balance of conductive additive and bonding agent; the modified positive active substance comprises 90-99wt% of positive active substances and 1-10wt% of blended electrode material; and the voltage platforms of the positive active substance and the blended electrode material are different. When the charge voltage platform of the selected electrode material is higher than the voltage platform of the positive active substance, a protection effect can be taken for an over-charge behavior. When the discharge voltage platform of the selected blended electrode material is lower than the voltage platform of the positive active substance, a protection effect can be taken for an over-discharge behavior. The positive electrode containing the blended electrode material as well as the negative electrode, the diaphragm, the electrolyte and the outer package are assembled to form the lithium ion battery, and the over-charge and over-discharge safety of a lithium ion battery pack is protected by a charge/discharge protection circuit device.
Description
Technical field
The invention belongs to the power lithium-ion battery technical field, the mistake that relates to lithium ion battery charges and discharge security protection technology, specifically, relates to a kind of power lithium-ion battery with the safeguard protection of charging and discharging and preparation method thereof.
Background technology
As current internationally recognized desirable chemical energy source, lithium ion battery has that volume is little, capacitance is big, the voltage advantages of higher, is widely used in electronic products such as mobile phone, laptop computer.Bigger development space is also brought to lithium ion battery in the electric automobile field that enlarges day by day.Lithium ion battery is considered to the most potential electrokinetic cell system because of its high voltage, high-energy-density, high power density and good high and low temperature flash-over characteristic.The fail safe of lithium ion battery at present is to restrict it to be applied to the bottleneck of dynamical system.Cross that to charge and discharge be one of safety problem that most probable is run in the lithium ion battery use, particularly in the process of lithium ion battery group work.
Overcharging the safety issue that causes mainly comes as for electrolytical decomposition.When battery is in when overcharging state, the lithium current potential that takes off of negative electrode rises rapidly with the increase of the degree of overcharging.When exceeding the electrolyte electrochemical stability window; Irreversible oxidation Decomposition will take place at cathode surface in organic electrolyte solution, produces imflammable gas, emits big calorimetric simultaneously; Cause battery temperature and interior the pressure sharply to be risen, thereby cause a series of exothermic reactions.When internal temperature of battery was increased to 120 ℃, the SEI film began to decompose, and the embedding lithium carbon electrode that exposes will further react with electrolyte, emit more heat and gas.Along with the further rising of temperature, the oxygen uptake decomposition reaction also can take place in cathode material, produces a large amount of heats.At short notice the accumulated inside of battery a large amount of heat, finally cause the battery thermal runaway, blast or burn.In addition, be unlikely to produce serious security incident, but be in when putting state when battery, destroy the structure of battery active material probably, cause battery performance to worsen and destroy or the shortening in useful life though cross to put.This also need do one's utmost to be avoided in actual application.
For the mistake that guarantees lithium ion battery charges and discharge fail safe, in practical application, all can prepare special-purpose protective circuit to single battery and battery pack and carry out management of charging and discharging.This method is direct, effective, but is not what be perfectly safe.Particularly concerning power battery pack,, realize all effectively controlling with management difficulty also bigger to every battery because battery pack normally is made up of through serial or parallel connection a fairly large number of cell.Usually, when battery took place to charge and discharge, cell voltage changed often very fast; In the extremely short time just security incident might take place, in case the protective circuit inefficacy, or detection sensitivity is low excessively; Uncontrollable its overcharges to let pass, and just brings serious safety problem most probably.Therefore, except exploitation overcharges discharge protection circuit more efficiently, researchers are also exploring various possible mistakes always and are charging and discharging the protection new way.
At present, positive electrode, barrier film and electrolyte three aspects are that researchers carry out the main direction that overcharging resisting is put research.Select suitable positive electrode and material modified be to improve battery overcharging resisting effective methods.New types of diaphragm like the voltage-sensitive barrier film etc., when over-charging of battery, can be transformed into electronic conductor, makes to improve its fail safe thereby stop its voltage further to raise by internal short-circuit of battery, but at present still in development.The use of additive also is to improve an important leverage that overcharges fail safe in addition, but additive effect in actual application of research and development is all not ideal enough at present.
Summary of the invention
The purpose of this invention is to provide a kind of power lithium-ion battery and preparation method thereof with the safeguard protection of charging and discharging; This battery is in positive electrode active materials, to sneak into the different blending electrode material of voltage platform; If the charging voltage platform of blending electrode material is higher than the voltage platform of positive electrode active materials; When battery overcharged behavior, cell voltage can rise to the charging voltage platform of blending electrode material rapidly, thereby slowed down the speed that voltage raises; Overcharge discharge protection circuit and detect its magnitude of voltage with regard to time enough this moment, and its behavior of overcharging is controlled.In like manner; If the discharge voltage plateau of blending electrode material is lower than the voltage platform of positive electrode; When battery took place to put, cell voltage can be reduced to the discharge voltage plateau of blending electrode material rapidly, thereby slowed down the speed that voltage descends; Overcharge discharge protection circuit and detect its magnitude of voltage with regard to time enough this moment, and it is crossed clearance for controlling.This method is simple, but extensive use.
In order to achieve the above object; The invention provides a kind of power lithium-ion battery with the safeguard protection of charging and discharging; Comprise positive electrode and negative electrode, barrier film, electrolyte and external packing; Described positive electrode comprises the modification positive active material of percentage meter 90% ~ 95% by weight, and all the other are conductive agent and binding agent; This modification positive active material comprises 90 ~ 99% positive active material of percentage meter by weight and 1% ~ 10% blending electrode material; This positive active material is different with the voltage platform of blending electrode material.When the charging voltage platform of the blending electrode material of choosing is higher than the voltage platform of positive electrode active materials, the behavior of overcharging there is protection.When discharge voltage plateau is lower than the voltage platform of positive electrode active materials, let pass to protection is arranged to crossing.
The above-mentioned power lithium-ion battery with the safeguard protection of charging and discharging, wherein, described positive electrode comprises the conductive agent of percentage meter 3% ~ 5% by weight, and 2% ~ 5% binding agent.
The above-mentioned power lithium-ion battery with the safeguard protection of charging and discharging, wherein, the blending electrode material is selected the charging voltage platform material higher than positive active material, or the discharge voltage plateau material lower than positive active material, or above two kinds of mixing.
Above-mentioned power lithium-ion battery with the safeguard protection of charging and discharging; Wherein, described blending electrode material is selected any one in stratiform cobalt acid lithium and derivant material, stratiform lithium nickel cobalt dioxide and derivant material thereof, stratiform nickle cobalt lithium manganate and derivant material, lithium manganate having spinel structure and derivant material thereof, olivine-type LiFePO 4 and derivant material, spinel type lithium titanate and the derivant material thereof.
Above-mentioned power lithium-ion battery with the safeguard protection of charging and discharging; Wherein, described positive active material is selected any one in stratiform cobalt acid lithium and derivant material, stratiform lithium nickel cobalt dioxide and derivant material thereof, stratiform nickle cobalt lithium manganate and derivant material, lithium manganate having spinel structure and derivant material thereof, olivine-type LiFePO 4 and the derivant material thereof.
The present invention also provides a kind of preparation method according to the above-mentioned power lithium-ion battery with the safeguard protection of charging and discharging, and this method comprises following concrete steps:
Step 1, the preparation positive electrode: positive active material is mixed with the blending electrode material, and with conductive agent, binding agent; In the N-methyl pyrrolidone, disperse; Form slurry, then above-mentioned slurry is coated on the aluminium foil, 120 ℃ of vacuumizes obtained positive electrode in 24 hours;
Step 2, the preparation negative electrode: negative electrode active material, conductive agent, binding agent are disperseed in the N-methyl pyrrolidone, form slurry, then above-mentioned slurry is coated on the Copper Foil, 120 ℃ of vacuumizes obtained negative electrode in 24 hours;
Step 3, cutting positive electrode, negative electrode are wound into electric core with barrier film, in the battery case of packing into, again shell and cover plate are used package sealing with laser; Add the organic electrolyte that contains lithium ion from liquid injection hole, process column lithium ion battery.
Described protective circuit charges and discharge any one in the protective circuit for all are applicable to power lithium-ion battery.
The beneficial effect that the present invention had is:
1) owing in positive electrode, added the blending electrode material different with positive electrical active material voltage platform; Make when charging and discharging excessively; Slowed down the speed that voltage rises or descends; Provide more time that its voltage is detected and analyzes for overcharging discharge protection circuit, avoided because the rapid variation of voltage causes battery to damage or accident takes place.
2) selected blending electrode material is common electroactive material.Therefore, this technology is simple.
Embodiment
Describe in detail below according to the preferred embodiment of the invention,, omitted associated components of the prior art or process in the description, and omit description these well-known components or process for the ease of describing and outstanding the present invention.
Embodiment 1
Ferrousphosphate lithium material and lithium manganate material is even according to the mixed of 95.5:4.5, the mixed material with 92%, 2% microspheroidal superconduct carbon black, 2% CNT and 4% polyvinylidene fluoride disperse in the N-methyl pyrrolidone, form slurry.Then above-mentioned slurry is coated on the aluminium foil, 120 ℃ of vacuumizes obtained positive electrode in 24 hours.
Carbonaceous mesophase spherules with 94%, 2% microspheroidal superconduct carbon black, 2% CNT and 2% polyvinylidene fluoride disperse in the N-methyl pyrrolidone, form slurry.Then above-mentioned slurry is coated on the Copper Foil, 120 ℃ of vacuumizes obtained negative electrode in 24 hours.
Positive plate (being positive electrode) and negative plate (being negative electrode) are cut into suitable dimensions, are wound into electric core, in the battery case of packing into, again shell and cover plate are used package sealing with laser with diaphragm paper.Add the organic electrolyte that 5 grams contain lithium ion from liquid injection hole, process cylindrical ferrous phosphate lithium battery.
Same process is made the battery pack that the battery obtain is formed 5 strings, and this battery pack connected and charged and discharged the control protective device.When the monomer battery voltage in the battery pack during greater than 3.8V, voltage gathers way and slows down, and utilizes to charge and discharge the control protective device, cuts off charge circuit, and battery pack is played the over-charge protective effect.
Embodiment 2
Cobalt acid lithium material and lithium manganate material is even according to the mixed of 95:5, with material after 92% the mixing, 2% microspheroidal superconduct carbon black, 2% CNT and 4% polyvinylidene fluoride disperse in the N-methyl pyrrolidone, form slurry.Then above-mentioned slurry is coated on the aluminium foil, 120 ℃ of vacuumizes obtained positive electrode in 24 hours.
With 94% carbonaceous mesophase spherules, 2% microspheroidal superconduct carbon black, 2% CNT and 2% polyvinylidene fluoride disperse in the N-methyl pyrrolidone, form slurry.Then slurry is coated on the aluminium foil, 120 ℃ of vacuumizes obtained negative electrode in 24 hours.
Positive plate and negative plate are cut into suitable dimensions, are wound into electric core, in the battery case of packing into, again shell and cover plate are used package sealing with laser with barrier film.Add the organic electrolyte that 5 grams contain lithium ion from liquid injection hole, leave standstill, make electrolyte fully soak into the solid particle on the aluminium foil.Discharge through charge and discharge first and with the gas that produces in the charge and discharge process first, and sealing exhaust body passage, cobalt acid lithium battery obtained.
Same process is made the battery pack that the battery obtain is formed 10 strings, and this battery pack connected and charged and discharged the control protective device.When the monomer battery voltage in the battery pack during greater than 4.2V, voltage gathers way and slows down, and utilizes to charge and discharge the control protective device, cuts off charge circuit, and battery pack is played the over-charge protective effect.
Embodiment 3
It is even that lithium manganate material and lithium titanate material are pressed the 94:6 mixed, the mixed material with 90%, and 2.5% microspheroidal superconduct carbon black, 2.5% CNT and 5% polyvinylidene fluoride disperse in the N-methyl pyrrolidone, form slurry.Then above-mentioned solidliquid mixture is coated on the aluminium foil, 120 ℃ of vacuumizes obtained positive electrode in 24 hours.
With 94% carbonaceous mesophase spherules, 2% microspheroidal superconduct carbon black, 2% CNT and 2% polyvinylidene fluoride disperse in the N-methyl pyrrolidone, form slurry.Then above-mentioned solidliquid mixture is coated on the aluminium foil, 120 ℃ of vacuumizes obtained negative electrode in 24 hours.
Positive plate and negative plate are cut into suitable dimensions, are wound into electric core, in the battery case of packing into, again shell and cover plate are used package sealing with laser with barrier film.Add the organic electrolyte that 5 grams contain lithium ion from liquid injection hole, leave standstill, make electrolyte fully soak into the solid particle on the aluminium foil.Discharge through charge and discharge first and with the gas that produces in the charge and discharge process first, and sealing exhaust body passage, lithium manganate battery obtained.
Same process is made the battery pack that the battery obtain is formed 10 strings, and this battery pack connected and charged and discharged the control protective device.When the monomer battery voltage in the battery pack discharged less than 2V, the voltage decrease speed slowed down, and utilized to charge and discharge the control protective device, cut off discharge loop, battery pack is risen to be put protective effect.
Although content of the present invention has been done detailed introduction through above-mentioned preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple modification of the present invention with to substitute all will be conspicuous.Therefore, protection scope of the present invention should be limited appended claim.
Claims (6)
1. power lithium-ion battery with the safeguard protection of charging and discharging; Comprise positive electrode and negative electrode, barrier film, electrolyte and external packing; It is characterized in that described positive electrode comprises the modification positive active material of percentage meter 90% ~ 95% by weight, all the other are conductive agent and binding agent; This modification positive active material comprises 90 ~ 99% positive active material of percentage meter by weight and 1% ~ 10% blending electrode material; This positive active material is different with the voltage platform of blending electrode material.
2. the power lithium-ion battery with the safeguard protection of charging and discharging as claimed in claim 1 is characterized in that, described positive electrode comprises the conductive agent of percentage meter 3% ~ 5% by weight, and 2% ~ 5% binding agent.
3. the power lithium-ion battery with the safeguard protection of charging and discharging as claimed in claim 1; It is characterized in that; The blending electrode material is selected the charging voltage platform material higher than positive active material, or the discharge voltage plateau material lower than positive active material, or above two kinds of mixing.
4. the power lithium-ion battery with the safeguard protection of charging and discharging as claimed in claim 3; It is characterized in that described blending electrode material is selected any one in stratiform cobalt acid lithium and derivant material, stratiform lithium nickel cobalt dioxide and derivant material thereof, stratiform nickle cobalt lithium manganate and derivant material, lithium manganate having spinel structure and derivant material thereof, olivine-type LiFePO 4 and derivant material, spinel type lithium titanate and the derivant material thereof.
5. like any described power lithium-ion battery among the claim 1-4 with the safeguard protection of charging and discharging; It is characterized in that described positive active material is selected any one in stratiform cobalt acid lithium and derivant material, stratiform lithium nickel cobalt dioxide and derivant material thereof, stratiform nickle cobalt lithium manganate and derivant material, lithium manganate having spinel structure and derivant material thereof, olivine-type LiFePO 4 and the derivant material thereof.
6. preparation method with power lithium-ion battery of the safeguard protection of charging and discharging according to claim 1 is characterized in that this method comprises following concrete steps:
Step 1, the preparation positive electrode: positive active material is mixed with the blending electrode material, and with conductive agent, binding agent; In the N-methyl pyrrolidone, disperse; Form slurry, then above-mentioned slurry is coated on the aluminium foil, 120 ℃ of vacuumizes obtained positive electrode in 24 hours;
Step 2, the preparation negative electrode: negative electrode active material, conductive agent, binding agent are disperseed in the N-methyl pyrrolidone, form slurry, then above-mentioned slurry is coated on the Copper Foil, 120 ℃ of vacuumizes obtained negative electrode in 24 hours;
Step 3, cutting positive electrode, negative electrode are wound into electric core with barrier film, in the battery case of packing into, again shell and cover plate are used package sealing with laser; Add the organic electrolyte that contains lithium ion from liquid injection hole, process column lithium ion battery.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012101938462A CN102709530A (en) | 2012-06-13 | 2012-06-13 | Power lithium ion battery with over-charge and over-discharge protection function and preparation method thereof |
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| CN2012101938462A CN102709530A (en) | 2012-06-13 | 2012-06-13 | Power lithium ion battery with over-charge and over-discharge protection function and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103296304A (en) * | 2013-05-03 | 2013-09-11 | 浙江超威创元实业有限公司 | Lithium ion battery with improved over charge performance |
| CN104347846A (en) * | 2013-07-26 | 2015-02-11 | 浙江南博电源科技有限公司 | Preparation method for safety-improved nickel-cobalt lithium manganate positive electrode sheet |
| CN105449756A (en) * | 2015-07-31 | 2016-03-30 | 上海卫星工程研究所 | Automatic management system for lithium ion storage battery pack power supply sub system for satellite |
| CN109588056A (en) * | 2016-08-04 | 2019-04-05 | 通用汽车环球科技运作有限责任公司 | It prevents based on Li4Ti5O12Li-ion batteries piles overdischarge cathode compositions |
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| CN101404329A (en) * | 2008-05-20 | 2009-04-08 | 龚思源 | Phosphate and lithium titanate composite anode material for lithium ion battery and method for producing the same |
| CN102456912A (en) * | 2010-12-31 | 2012-05-16 | 深圳市海盈科技有限公司 | Lithium iron phosphate lithium ion battery and electric quantity state detection method and pairing method thereof |
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| CN1534821A (en) * | 2003-03-28 | 2004-10-06 | ������������ʽ���� | Non-aqueous electrolyte cell |
| CN101232095A (en) * | 2008-02-02 | 2008-07-30 | 广州市鹏辉电池有限公司 | Lithium ion battery positive pole active materials and battery |
| CN101404329A (en) * | 2008-05-20 | 2009-04-08 | 龚思源 | Phosphate and lithium titanate composite anode material for lithium ion battery and method for producing the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103296304A (en) * | 2013-05-03 | 2013-09-11 | 浙江超威创元实业有限公司 | Lithium ion battery with improved over charge performance |
| CN104347846A (en) * | 2013-07-26 | 2015-02-11 | 浙江南博电源科技有限公司 | Preparation method for safety-improved nickel-cobalt lithium manganate positive electrode sheet |
| CN105449756A (en) * | 2015-07-31 | 2016-03-30 | 上海卫星工程研究所 | Automatic management system for lithium ion storage battery pack power supply sub system for satellite |
| CN105449756B (en) * | 2015-07-31 | 2018-02-06 | 上海卫星工程研究所 | The autonomous management system of satellite lithium-ions battery group power subsystem |
| CN109588056A (en) * | 2016-08-04 | 2019-04-05 | 通用汽车环球科技运作有限责任公司 | It prevents based on Li4Ti5O12Li-ion batteries piles overdischarge cathode compositions |
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Application publication date: 20121003 |