CN102368551A - Lithium ion battery cathode material and lithium ion battery - Google Patents
Lithium ion battery cathode material and lithium ion battery Download PDFInfo
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- CN102368551A CN102368551A CN2011102789780A CN201110278978A CN102368551A CN 102368551 A CN102368551 A CN 102368551A CN 2011102789780 A CN2011102789780 A CN 2011102789780A CN 201110278978 A CN201110278978 A CN 201110278978A CN 102368551 A CN102368551 A CN 102368551A
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- lithium ion
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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 invention provides a lithium ion battery cathode material with stable high temperature performance comprising more than 23 % of nickel. The microscopic particle appearance of the material is characterized in that primary particles aggregate into secondary quasi-spherical particles as shown in an SEM-graph. By controlling the sizes of the primary particles which form the secondary quasi-spherical particles, the lithium ion battery cathode material with stable high temperature performance can be obtained. The invention also provides a lithium ion battery using the material. The lithium ion battery has the advantages of high volumetric specific energy and good high temperature performance.
Description
Technical field
The lithium ion battery that the present invention relates to anode material for lithium ion battery and use this positive electrode to process.
Background technology
Lithium ion battery is since 1991 become commercialized, and its used positive electrode is also being updated.The positive electrode that is used for lithium ion battery the earliest mainly is a cobalt acid lithium, and its major defect is that price is high, and capacity is lower than lithium nickel cobalt dioxide.Developed some novel positive electrodes for this reason and mainly contained following several kinds: LiMn2O4, nickle cobalt lithium manganate and lithium nickel cobalt dioxide.Its performance and cobalt acid lithium are following:
1, gram volume:
About spinel lithium manganate 100 MAHs, cobalt acid lithium is about 140 MAHs, about ternary material 140 MAHs, lithium nickel cobalt dioxide is about 180 MAHs.Gram volume is high more, and its weight energy density is high more.
2, compacted density
LiMn2O4 is about every cubic centimetre of 3.0 gram, and ternary material is about every cubic centimetre of 3.4 gram, and cobalt acid lithium 3.8 restrains about every cubic centimetre.Compacted density is high more, and its volume energy density is big more.
3, price
LiMn2O4 is minimum, and ternary material and lithium nickel cobalt dioxide are lower than the sour lithium of cobalt, and cobalt acid lithium price is the highest.
With regard to above index, it is low that the positive electrode that contains nickel has price, and capacity is high, the characteristics that cost performance is high.But find but that in actual application but there is the relatively poor problem of application performance in nickeliferous too much material.Be in particular in for too strictness of environmental requirement, increased production cost, the storge quality in the above environment of 60 degree of the lithium ion battery that the high material of while application of nickel content is worked it out is poor, and expansion rate is high, is difficult to reach the application request of lithium ion battery.For this reason, let the high positive electrode of nickel content, just must solve its high-temperature storage performance difference using the high problem of environmental requirement can practical application.
Thus, need more study to address the above problem, it is low to develop a kind of price, and capacity and platform are high, and the positive electrode that compacted density is high satisfies the requirement of lithium ion battery development.
Summary of the invention
To nickeliferous anode material for lithium ion battery bad application performance, gas production is big under hot environment, the problem that expansion rate is high.The inventor has done a large amount of research; Grope through what test many times; The beat all discovery of the inventor can provide a kind of higher specific capacity that has, lower production cost and the anode material for lithium ion battery of excellent high through controlling nickeliferous anode material for lithium ion battery granular size.The inventor finds to work as for nickeliferous anode material for lithium ion battery; When nickel content 24% above the time; The meso-position radius of its granularity is greater than 2 microns, and analyzing it from Electronic Speculum figure, to form its granule-morphology be not the secondary ball type that is agglomerated into of granule and when being single crystal grain. and this positive electrode has the good high-temperature storge quality.
Through a large amount of research and test; The inventor finds: the individual particle size is lower than in 20% in the ratio that accounts for total individual particle more than 1 micron in the primary particle that forms second particle in the nickeliferous positive electrode; This positive electrode is under the hot environment more than 60 degree; Expansion rate is high, and storge quality is poor.
Serious expansion will take place in the battery of working it out with this positive electrode when 60 spend above high-temperature storage.The high-temperature storage performance is poor.Granularity through the control nickel-containing material can obtain the anode material for lithium ion battery that high-temperature behavior is more stable, Capacity Ratio is higher, cost is lower thus.
The positive electrode that present lithium ion battery is used, the ternary material compacted density is low, and platform is low.Nickel-containing material gas production under hot environment is big, and expansion rate is high, and platform is low low with compacted density.Cobalt acid lithium price is too high.Depend merely on the demand that these materials have satisfied not growing lithium ion battery.
Compare with aforementioned prior art; The inventor finds: be higher than the positive electrode more than 23% for nickel content; The meso-position radius of its granularity is greater than 6 microns; And in more than 20%, this positive electrode has the good high-temperature storge quality to the individual particle size in the ratio that accounts for total individual particle more than 1 micron from primary particle of its formation secondary spherical particle of Electronic Speculum figure analysis.
In the present invention, a kind of lithium ion secondary battery anode material is provided, this positive electrode is that nickel content is at the positive electrode more than 23.The principal character of this material is that the meso-position radius of its granularity is greater than 6 microns; And in more than 20%, this positive electrode has the good high-temperature storge quality to the individual particle size in the ratio that accounts for total individual particle more than 1 micron from primary particle of its formation secondary spherical particle of Electronic Speculum figure analysis.
The present invention simultaneously also provides a kind of lithium ion battery, and the employed positive electrode of this lithium ion battery is a material provided by the present invention, and it for example comprises with the lower part: electrode, electrolyte, barrier film, container.Wherein electrode comprises positive pole and negative pole, and positive pole comprises the anode collection device and is coated in the positive active material on the anode collection device; Negative pole comprises the negative pole currect collecting device and is coated in the negative electrode active material layer on the negative pole currect collecting device; Barrier film can be that simple solid insulating layer also can be the decorating film with electric conductivity; Container is positive pole, negative pole, barrier film, electrolytical inclusion body.
The concrete mode of embodiment of the present invention
Below more specifically introduce secondary lithium battery cover plate that is applicable to the inventive method and the secondary lithium battery that has this cover plate with non-limited way.
Positive electrode among the present invention is meant that nickel content is more than 24% at least; The principal character of this material be the meso-position radius of its granularity greater than 6 microns, and from Electronic Speculum figure analyze its primary particle that forms the secondary spherical particle individual particle size in the ratio that accounts for total individual particle more than 1 micron more than 20%.
The preparation of positive electrode can for example following method among the present invention.
Can presoma that contain nickel and lithium carbonate be mixed 850 degree sintering 24 hours, pulverize with mortar afterwards.
Produce following lithium ion battery with the prepared positive electrode that comes out as active material.
The general structure of secondary lithium battery comprises: positive pole, negative pole, nonaqueous electrolyte and with positive pole and negative pole barrier film spaced apart from each other.The metal lithium salts of nonaqueous electrolyte through will containing lithium for example LiPF6 obtains in the nonaqueous solvents of for example ethylene carbonate or dimethyl carbonate as electrolyte dissolution.Barrier film does not dissolve in above-mentioned nonaqueous solvents, and is the perforated membrane of being processed by for example polyethylene or acrylic resin.It also can be the solid electrolyte that contains the gel electrolyte type that obtains by the non-aqueous electrolytic solution plasticized polymeric material.
Anodal
Anodal preparation can for example be adopted through positive electrode active materials, conductive agent and adhesive are mixed the slurry of processing in appropriate solvent and be coated on collector for example on the aluminium foil, and is then dry and be pressed into pole piece.
Battery positive electrode active material is that the meso-position radius of its granularity is greater than 6 microns for nickel content at least in the principal character of this material more than 24% among the present invention; And from Electronic Speculum figure analyze its primary particle that forms the secondary spherical particle individual particle size in the ratio that accounts for total individual particle more than 1 micron in more than 20%.
In addition, the present invention can use known conductive agent and adhesive.The mixed proportion of each component can be used known proportion in the positive electrode active materials.
Barrier film
The used barrier film of the present invention can be known barrier film, for example can be by nonwoven fabrics, polyethylene porous membrane or the polypropylene porous film of synthetic resin and the type of being processed by the material that this type material is composited.
Negative pole
Negative pole preparation can for example be adopted through negative active core-shell material, conductive agent and adhesive are mixed in appropriate solvent and stir the slurry of processing and be coated on collector for example on the Copper Foil, then drying and be pressed into pole piece.
Battery cathode active substance is the material that carbon is and non-carbon is that lithium ion can embed therein and deviate among the present invention, comprise, for example, lithium alloy (for example, Li
4Ti
5O
12), metal oxide (for example amorphous state tin oxide, WO
2And MoO
2), TiS
2And the carbon that can embed and deviate from lithium ion is thing.It is that thing serves as negative active core-shell material that carbon is used in special hope.
The used carbon of the present invention is that thing comprises, for example, and graphite, non orientation graphite, coke, carbon fiber, spherical carbon, resin sintered carbon and vapor grown carbon, CNT.Show high recharge efficiency because comprise the negative pole of aforesaid particular carbon fiber or spherical carbon, special hope uses mesophase pitch-based carbon fibers or the spherical carbon of mesophase pitch base to serve as carbonaceous material.The spherical carbon of mesophase pitch-based carbon fibers and mesophase pitch base can adopt known method to obtain.
Nonaqueous electrolyte can adopt known type and material; Do not limit especially; Nonaqueous electrolyte; For example can use dissolving electrolyte in nonaqueous solvents and the liquid nonaqueous electrolyte processed, polymer, nonaqueous solvents and dissolved matter is the compound and colloid nonaqueous electrolyte processed, polymer solids nonaqueous electrolyte or the like.
The structure of battery can be through reeling or the mode of lamination forms, and for example can process column, shape such as square.
Container:
The container of the secondary lithium battery just battery cover of secondary lithium battery adopts the battery cover that has insulating barrier and lug fairlead of the present invention.Battery case adopts common metal-back.The operation that discharges and recharges to battery adopts mode well known in the art to carry out.
Embodiment
To be described in detail the present invention according to concrete result of the test below.
Presoma and the lithium carbonate that will contain nickel was blended under the air atmosphere 850 degree sintering 24 hours, pulverized with mortar afterwards, processed positive pole and used active material.
Adopt the collector of Copper Foil as negative pole, aluminium foil is as the collector of positive pole, and the sour lithium of cobalt that goes out with institute's sintering is as positive active material usefulness, and negative electrode active material is used MCMB.Battery size is a square 633770.Cobalt acid lithium is mixed with 5% adhesive PVDF and 4% conductive carbon black, in 1: 1 ratio adding N-methyl pyrrolidone.Negative material can directly mix with 10% adhesive PVDF, adds in 1: 1 ratio, processes slurry.The anode sizing agent that to become reconciled is coated on the anodal collector with the method that applies, and cathode size is coated on the negative current collector, oven dry then, compacting.Positive/negative plate point after the compacting is gone up lug, behind the insertion barrier film (barrier film is the PP material), pack into after on up-coiler, reeling in the aluminum hull, lug is drawn the back lug fairlead is sealed with glue.As the experiment contrast example, the battery cover that it adopted is that the aluminum cell lid that has rivet is processed.Battery case and battery cover welded seal are in the same place.Carry out fluid injection in relative humidity under less than 1.5% environment, electrolyte adopts EC: DEC: DMC=1: 1: 1 mixed solvent, electrolyte is the 1M lithium hexafluoro phosphate, seals immediately after the fluid injection.
Comparative Examples 1:
Process a plurality of lithium ion batteries of 633770 squares as stated above; Used cell active materials be the meso-position radius of 442 its granularities greater than 6 microns, and from Electronic Speculum figure analyze its primary particle that forms the secondary spherical particle individual particle size in the ratio that accounts for total individual particle more than 1 micron less than 10%.The battery of being made its cell expansion rate under 4 hours high-temperature storage condition of 85 degree is 37.8%.
Comparative Examples 2:
Process a plurality of lithium ion batteries of 633770 squares as stated above; Used cell active materials be the meso-position radius of 532 its granularities greater than 6 microns, and from Electronic Speculum figure analyze its primary particle that forms the secondary spherical particle individual particle size in the ratio that accounts for total individual particle more than 1 micron less than 10%.The battery of being made its cell expansion rate under 4 hours high-temperature storage condition of 85 degree is 37.8%.
Comparative Examples 1:
Process a plurality of lithium ion batteries of 633770 squares as stated above; Used cell active materials be the meso-position radius of 442 its granularities greater than 6 microns, and from Electronic Speculum figure analyze its primary particle that forms the secondary spherical particle individual particle size in the ratio that accounts for total individual particle more than 1 micron less than 10%.The battery of being made its cell expansion rate under 4 hours high-temperature storage condition of 85 degree is 37.8%.
Embodiment 1
Process a plurality of lithium ion batteries of 633770 squares as stated above; Used cell active materials be the meso-position radius of 532 its granularities greater than 6 microns, and from Electronic Speculum figure analyze its primary particle that forms the secondary spherical particle individual particle size in the ratio that accounts for total individual particle more than 1 micron greater than 18%.The battery of being made its cell expansion rate under 4 hours high-temperature storage condition of 85 degree is 7.8%.
Process a plurality of lithium ion batteries of 633770 squares as stated above, used cell active materials cobalt content is 40%, and nickel content is 13%.The pH value of used positive electrode is 11.3.The battery of being made its cell expansion rate under 4 hours high-temperature storage condition of 85 degree is 19.8%.
Embodiment 2
Process a plurality of lithium ion batteries of 633770 squares as stated above; Used cell active materials be the meso-position radius of 442 its granularities greater than 6 microns, and from Electronic Speculum figure analyze its primary particle that forms the secondary spherical particle individual particle size in the ratio that accounts for total individual particle more than 1 micron greater than 18%.The battery of being made its cell expansion rate under 4 hours high-temperature storage condition of 85 degree is 6.7%.
Above-mentioned experimental result shows; For containing nickel content at the anode material for lithium ion battery more than 23%, and the spherical oarse-grained positive electrode of the granule-morphology secondary class that to be granule form when the ratio that accounts for total primary particle less than 1 micron particle in the primary particle that forms second particle greater than 15% the time.This material has high-temperature storage performance preferably.
Claims (4)
1. anode material for lithium ion battery; Contain three kinds of elements of nickel cobalt manganese in this material; And the content of nickel element is more than 23%; The microscopic particles pattern of this material is seen as primary particle from SEM figure, and to be agglomerated into the secondary class spherical, and this material is characterised in that to be formed in the spherical primary particle of secondary class, sees that from SEM figure ratio that size accounts for total primary particle at 1 particle more than 1 micron is more than 15%.
2. nonaqueous electrolyte battery has and can insert and deviate from the positive pole that the negative pole that the lithium ion negative electrode active material constitutes and the positive active material that can insert and deviate from lithium ion constitute, and it is characterized in that used positive active material according to claim 1.
3. nonaqueous electrolyte battery; The positive pole that has the negative pole that can insert and deviate from lithium ion negative electrode active material formation and can insert and deviate from the positive active material formation of lithium ion; Used positive active material is characterized in that used nonaqueous electrolyte is from organic bath or polymer solid electrolyte, to choose in any according to claim 1.
4. like any described nonaqueous electrolyte battery in the 2-3 claim, it is characterized in that containing in the said solvent in the non-aqueous electrolytic solution the inferior ethyl of carbonic acid of 5%-25%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102789780A CN102368551A (en) | 2011-09-20 | 2011-09-20 | Lithium ion battery cathode material and lithium ion battery |
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|---|---|---|---|
| CN2011102789780A CN102368551A (en) | 2011-09-20 | 2011-09-20 | Lithium ion battery cathode material and lithium ion battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022499A (en) * | 2012-12-03 | 2013-04-03 | 东莞新能源科技有限公司 | Mixed positive-pole material for lithium ion battery |
| CN104466094A (en) * | 2013-09-18 | 2015-03-25 | 株式会社东芝 | Nonaqueous electrolyte battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010080394A (en) * | 2008-09-29 | 2010-04-08 | Sumitomo Metal Mining Co Ltd | Positive electrode active material for nonaqueous electrolyte secondary battery and manufacturing method therefor, and nonaqueous electrolyte secondary battery |
| CN102255068A (en) * | 2010-05-19 | 2011-11-23 | 孙杰 | Lithium ion battery anode material and lithium ion battery adopting the lithium ion battery anode material |
-
2011
- 2011-09-20 CN CN2011102789780A patent/CN102368551A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010080394A (en) * | 2008-09-29 | 2010-04-08 | Sumitomo Metal Mining Co Ltd | Positive electrode active material for nonaqueous electrolyte secondary battery and manufacturing method therefor, and nonaqueous electrolyte secondary battery |
| CN102255068A (en) * | 2010-05-19 | 2011-11-23 | 孙杰 | Lithium ion battery anode material and lithium ion battery adopting the lithium ion battery anode material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022499A (en) * | 2012-12-03 | 2013-04-03 | 东莞新能源科技有限公司 | Mixed positive-pole material for lithium ion battery |
| CN103022499B (en) * | 2012-12-03 | 2016-09-07 | 东莞新能源科技有限公司 | A kind of lithium ion battery blended anode material |
| CN104466094A (en) * | 2013-09-18 | 2015-03-25 | 株式会社东芝 | Nonaqueous electrolyte battery |
| CN104466094B (en) * | 2013-09-18 | 2017-04-12 | 株式会社东芝 | Nonaqueous electrolyte battery |
| US10374220B2 (en) | 2013-09-18 | 2019-08-06 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte battery |
| US11183680B2 (en) | 2013-09-18 | 2021-11-23 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte battery |
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Application publication date: 20120307 |