CN100527483C - Surface film coating modify method for improving lithium ionic cell positive pole safety - Google Patents
Surface film coating modify method for improving lithium ionic cell positive pole safety Download PDFInfo
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- CN100527483C CN100527483C CNB2007101198185A CN200710119818A CN100527483C CN 100527483 C CN100527483 C CN 100527483C CN B2007101198185 A CNB2007101198185 A CN B2007101198185A CN 200710119818 A CN200710119818 A CN 200710119818A CN 100527483 C CN100527483 C CN 100527483C
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- sputtering
- pole piece
- plated film
- cell positive
- positive pole
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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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Abstract
The present invention relates to a technology of filming on the anode surface of a lithium-ion battery by the magnetic control sputtering method. The positive plate of the common lithium-ion battery is gained through film preparation and is cut into the needed size and put to a sample chamber of a magnetic control sputtering device; a proper target material is put to a sputtering chamber of the magnetic control sputtering device; the sputtering power is set between 40 W and 60 W and the sputtering time is set between 2 min and 30 min and then the positive plate is gained through filming. The positive plate has better cycle performance, charge-discharge capacity and thermal stability, and improves the safety performance of the lithium-ion battery under the conditions of overcharge, overdischarge and misuse.
Description
Technical field
The present invention relates to the anode material for lithium-ion batteries technology, be specially a kind of film plating process of anode material for lithium-ion batteries.
Background technology
Along with the continuous development of electronic technology, promoted developing rapidly of high-performance, environmental friendliness secondary cell.Lithium ion battery is positive and negative secondary cell with different lithium intercalation compounds, general cobalt acid lithium, lithium nickelate and LiMn2O4 and their modified compound of adopting is as positive pole, adopting lithium to insert carbon compound as negative pole, is that electrolyte is formed battery with the organic solution that is dissolved with lithium salts.In charge and discharge process, Li
+Between the two poles of the earth, come and go embedding and take off discharging and recharging of embedding realization battery.It has many advantages, its specific energy height, characteristics such as the life-span is long, self discharge is little, safety and environmental friendliness have received special concern, since lithium ion battery comes into the market in portable development, keep development fast, be that the sales volume or the market sales revenue all improve a lot always.
But in recent years lithium ion battery be under abuse conditions (put, short circuit, vibration, extruding etc.) as heating, overcharge, crossing can occur catching fire, incidents such as blast and even injury to personnel.So the fail safe of lithium ion battery causes people's extensive concern.The specific energy height of battery, and electrolyte mostly is organic combustibles etc. greatly when the generation speed of battery heat during greater than radiating rate, just safety issue may occur.Positive electrode is an important component part of lithium ion battery, in the lithium ion charge and discharge process, not only will provide back and forth embedding/needed lithium of the process of taking off in the both positive and negative polarity lithium intercalation compound, forms the needed lithium of SEI film but also will bear the negative material surface.The thermal stability of positive pole and electrolyte and between reaction be to close one of key factor of series lithium ion battery safety.
Summary of the invention
The objective of the invention is to be to provide a kind of by the technology of preparing of magnetically controlled sputter method to the based lithium-ion battery positive plate surface coating.Adopt the anode pole piece of the lithium ion battery of present technique preparation, make the reaction severe degree between lithium ion cell positive and the electrolyte reduce and improve its thermal stability, strengthen its overcharge, cross put and abuse conditions under security performance, have better cycle performance and longer useful life simultaneously.
Common anode pole piece generally is to be LiMO by active material
2(M is Co, Ni, Mn, a kind of among the Fe), LiNi
1-xCo
1-xo
2(0＜x＜1), LiMn
2O
4, LiNi
1/3Co
1/3Mn
1/3O
2Deng and they material modified in a kind ofly form by adding conductive agent acetylene black and binding agent Kynoar (PVDF) smear.
Technical scheme of the present invention is to adopt the method for magnetron sputtering, and sputtering time is 2min～30min, and sputtering power is 40W～60W, has generated the granular film of one deck on anodal surface.
The plated film target material is the high-temperature stability material, as Si, SiO
2, CaO, CaF, Al
2O
3, SiC, MgO, ZrO, FeO
xDeng.The preparation method may further comprise the steps:
(1) positive active material is LiMO
2(M is Co, Ni, Mn, a kind of among the Fe), LiNi
1-xCo
1-xo
2(0＜x＜1), LiMn
2O
4, LiNi
1/3Co
1/3Mn
1/3O
2Deng and they material modified in a kind of, conductive agent acetylene black, binding agent Kynoar (PVDF), by weight the mixed smear of 85:10:5, oven dry obtains not plated film pole piece;
(2) pole piece that coats in (1) is cut into the sample room that the required size of experiment is put into magnetron sputtering apparatus;
(3) target is put into the sputtering chamber of magnetron sputtering apparatus;
(4) adjust the numerical value of the air pressure of magnetron sputtering apparatus, set sputtering power and sputtering time to requirement of experiment;
(5) equipment of bringing into operation is the sample plated film, obtains the anode material for lithium-ion batteries of plated film modified.
By magnetically controlled sputter method is that the principle of anode slice of lithium ion battery plated film is: the coating chamber base vacuum degree of magnetron sputtering apparatus is extracted into 7.0 * 10
-3Below the Pa, charge into a certain proportion of working gas such as argon gas (Ar), nitrogen, oxygen etc., when reaching the desired vacuum degree of technology, the electronics that dissociates in the coating chamber, under effect of electric field, fly to pole piece, simultaneously owing to it prolong motion distance (being the magnetron pattern) to the constraint in target magnetic field.Electronics bumps (high potential position of pole piece in electric field) with the working gas atom in flying to the process of pole piece under the effect of crossed electric and magnetic field, and when having enough energy as if electronics, then ionization goes out cation and another electronics e, and electronics flies to pole piece.The cation that ionization goes out quickens to fly to sputtering target and with high-energy bombardment target surface, makes target generation sputter under electric field action, in sputtering particle, neutral target atom (or molecule) is deposited on the pole piece surface and forms film.
The adhesion that the invention has the beneficial effects as follows coatings and pole piece surface is strong, and is few to the pole piece surface breakdown, can prevent the pole piece oxidation under inert gas, coatings densification, even; And equipment is simple, and is easy to operate.Because the material of used target itself is very stable, can pernicious effect not take place to electrolyte simultaneously under high temperature and the above high voltage of 4V.So the reaction severe degree of anode pole piece behind the plated film and electrolyte significantly reduces, organic electrolyte decomposes minimizing, conductivity improves, battery is had follows bad performance, charge/discharge capacity, good thermal stability preferably, improved overcharge, cross put and abuse conditions under security performance.
Description of drawings
Fig. 1-a lithium ion cell positive is the sem photograph of plated film pole piece not,
B is to be the sem photograph of 5min pole piece the lithium ion cell positive plated film time,
C is to be the sem photograph of 10min pole piece the lithium ion cell positive plated film time,
D is to be the sem photograph of 15min pole piece the lithium ion cell positive plated film time;
Fig. 2-lithium ion cell positive plated film time is the energy spectrum analysis figure and the constituent content ratio chart of the ESEM of 15min pole piece;
Fig. 3-anodal plated film pole piece compares with the pole piece first charge-discharge that is untreated;
Fig. 4-a compares for the plated film pole piece among the embodiment 1 and the pole piece preceding ten all discharge capacities that are untreated,
B compares for the plated film pole piece among the embodiment 1 and the pole piece preceding ten all cycle efficienies that are untreated.
Embodiment
The invention will be further described below in conjunction with accompanying drawing and example.
Select the active material of 0.2g lithium cobalt oxygen for use as positive electrode, add 0.0235g conductive agent acetylene black and be put into that to add 0.0117g binding agent Kynoar (PVDF) in the mortar again be the solvent of binding agent with N-methyl-2-pyridine alkane ketone, the three is blended into slurry at normal temperatures and pressures, evenly coat on the aluminum substrates as collector, resulting film thickness is about 40 μ m, behind 55 ℃ of vacuumize 12h, under 0.2MPa, compress, will drying by the fire good pole piece then, to be cut into 20 * 20mm standby.Put into the sample room of magnetron sputtering apparatus cutting out good pole piece.With SiO
2Target is put into the sputtering chamber of magnetron sputtering apparatus.The air pressure of adjustable magnetic control sputtering equipment is transferred to 40W to power to 0.5Pa.It is that the 5min equipment of bringing into operation is the sample plated film that sputtering time is set.See Fig. 1, Fig. 2, Fig. 3, shown in Figure 4.
The standby anode pole piece of 20 * 20mm that is coated among the embodiment 1 is put into the sample room of magnetron sputtering apparatus.With the CaO target is the sputtering chamber that target is put into magnetron sputtering apparatus.The air pressure of adjustable magnetic control sputtering equipment is transferred to 40W to power to 0.5Pa.It is that the 5min equipment of bringing into operation is the sample plated film that sputtering time is set.
Embodiment 3
The standby anode pole piece of 20 * 20mm that is coated among the embodiment 1 is put into the sample room of magnetron sputtering apparatus.With Al
2O
3Target is the sputtering chamber that target is put into magnetron sputtering apparatus.The air pressure of adjustable magnetic control sputtering equipment is transferred to 40W to power to 0.5Pa.It is that the 10min equipment of bringing into operation is the sample plated film that sputtering time is set.
Analyzing accompanying drawing can know, can see that through the lithium ion cell electrode pole piece behind the magnetron sputtering plating surface generates coatings.Adopt the positive pole of this side's preparation to form diaphragm on the primary electrode surface, this film is stable, is overlying on electrode surface uniformly.Can also know that from accompanying drawing pole piece cycle performance, specific capacity, useful life and thermal stability behind the plated film all are improved.
Claims (3)
1, a kind of surface coating decoration method that improves lithium ionic cell positive pole safety, it is characterized in that: described method is to adopt the method for magnetron sputtering, sputtering target material is the high-temperature stability material, sputtering time is 2min～30min, sputtering power is 40W～60W, generates coatings on anodal surface.
2, a kind of a kind of surface coating decoration method that improves lithium ionic cell positive pole safety as claimed in claim 1, it is characterized in that: the high-temperature stability material is Si, SiO
2, CaO, CaF, Al
2O
3, SiC, MgO, ZrO, FeO
xIn one or more.
3, a kind of a kind of surface coating decoration method that improves lithium ionic cell positive pole safety as claimed in claim 1 is characterized in that may further comprise the steps:
(1) positive active material is LiMO
2, M is Co, Ni, Mn, a kind of, LiNi among the Fe
1-xCo
1-xo
2, wherein, 0＜x＜1, LiMn
2O
4, LiNi
1/3Co
1/3Mn
1/3O
2And a kind of, the conductive agent acetylene black in they material modified, binding agent Kynoar (PVDF), by weight the mixed smear of 85:10:5, oven dry obtains not plated film pole piece;
(2) pole piece that coats in (1) is cut into the sample room that the required size of experiment is put into magnetron sputtering apparatus;
(3) target is put into the sputtering chamber of magnetron sputtering apparatus;
(4) adjust the numerical value of the air pressure of magnetron sputtering apparatus, set sputtering power and sputtering time to requirement of experiment;
(5) equipment of bringing into operation is the sample plated film, obtains the anode material for lithium-ion batteries of plated film modified.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101198185A CN100527483C (en) | 2007-07-31 | 2007-07-31 | Surface film coating modify method for improving lithium ionic cell positive pole safety |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101198185A CN100527483C (en) | 2007-07-31 | 2007-07-31 | Surface film coating modify method for improving lithium ionic cell positive pole safety |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101162774A CN101162774A (en) | 2008-04-16 |
| CN100527483C true CN100527483C (en) | 2009-08-12 |
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ID=39297647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101198185A Expired - Fee Related CN100527483C (en) | 2007-07-31 | 2007-07-31 | Surface film coating modify method for improving lithium ionic cell positive pole safety |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9553306B2 (en) * | 2011-04-19 | 2017-01-24 | Toyota Jidosha Kabushiki Kaisha | Lithium secondary battery |
| CN102299316A (en) * | 2011-09-08 | 2011-12-28 | 浙江吉能电池科技有限公司 | Layered oxide lithium ion battery anode and preparation method thereof |
| CN102427119A (en) * | 2011-12-02 | 2012-04-25 | 中国科学院上海微系统与信息技术研究所 | Method for continuously coating on lithium ion battery membrane |
| CN108615861B (en) * | 2018-03-29 | 2021-08-31 | 深圳市德方纳米科技股份有限公司 | Modified lithium ion battery positive electrode material, preparation method thereof and lithium ion battery comprising modified lithium ion battery positive electrode material |
| CN108390013A (en) * | 2018-04-17 | 2018-08-10 | 安庆师范大学 | A kind of lithium ion battery electrode material nano surface metal-modified method |
| CN110660960B (en) * | 2018-06-29 | 2021-10-22 | 宁德时代新能源科技股份有限公司 | Battery and preparation method thereof |
| CN108923019B (en) * | 2018-06-30 | 2021-05-25 | 深圳市神火照明有限责任公司 | Preparation method of lithium ion battery anode material based on magnetron sputtering method |
| CN111224068A (en) * | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Metal lithium cathode for lithium battery and lithium battery |
| CN109768284A (en) * | 2019-03-11 | 2019-05-17 | 江南大学 | A kind of lithium-sulfur cell standalone functionality interlayer and preparation method thereof |
| CN110429241B (en) * | 2019-08-29 | 2021-01-12 | 桑顿新能源科技(长沙)有限公司 | Lithium battery anode, preparation method thereof, lithium battery, power supply system and electric equipment |
-
2007
- 2007-07-31 CN CNB2007101198185A patent/CN100527483C/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 用溶胶凝胶法在LiNi0.8Co2O2表面包覆SiO2. 应皆荣，万春荣，姜长印.电源技术，第25卷第6期. 2001 * |
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|---|---|
| CN101162774A (en) | 2008-04-16 |
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Granted publication date: 20090812 Termination date: 20100731 |