CN102306830B - Nickel-cobalt lithium manganate and lithium titanate system lithium ion battery with high-performance electrolyte solution - Google Patents
Nickel-cobalt lithium manganate and lithium titanate system lithium ion battery with high-performance electrolyte solution Download PDFInfo
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- CN102306830B CN102306830B CN201110239541.6A CN201110239541A CN102306830B CN 102306830 B CN102306830 B CN 102306830B CN 201110239541 A CN201110239541 A CN 201110239541A CN 102306830 B CN102306830 B CN 102306830B
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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
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Abstract
The invention discloses a nickel-cobalt lithium manganate and lithium titanate system lithium ion battery. The cathode material of the battery consists of nickel-cobalt lithium manganate, an adhesive 3 and a conducting agent; the anode material of the battery consists of lithium titanate, the adhesive and the conducting agent; the electrolyte solution comprises electrolyte and a solvent; and the electrolyte is LiPF6 or consists of the LiPF6 and lithium bis(oxalate)borate. In the nickel-cobalt lithium manganate and lithium titanate system lithium ion battery, the electrolyte solution has a wide using temperature range and high chemical stability and is suitable for the lithium ion battery of a nickel-cobalt lithium manganate and lithium titanate system. The lithium ion battery has high safety and long cycle life.
Description
Technical field
The present invention relates to a kind of lithium ion battery, particularly a kind of nickle cobalt lithium manganate and lithium titanate system lithium ion battery.
Background technology
Lithium ion battery is according to the difference of positive battery material, and lithium ion battery can be divided into cobalt acid lithium battery, lithium manganate battery, ternary material battery, ferrous phosphate lithium battery, other lithium material battery.The gram volume of nickle cobalt lithium manganate is high, and cycle performance is good, is to manufacture the good positive electrode of lithium-ion-power cell.
Using graphite in negative pole main raw material(s) lithium ion battery, graphite, electrolyte react on solid-liquid phase interface, form and are covered in one deck passivation layer of electrode surface.This layer of passivation layer can prevent that the large molecule of solvent from embedding negative pole, and causes peeling off of negative material.When electrolyte solvent contains PC, the SEI film of generation is can not coated electrode whole, and electrode material easily peels off in circulation.
Lithium titanate material is the lithium secondary battery cathode material of a kind of high-performance, high magnification type.Embed or deviate from process at Li, crystal formation does not change, change in volume is less than 1%, therefore be called as " zero strain material ", this is significant, can avoid in charge and discharge cycles because the flexible back and forth of electrode material causes structural damage, thereby cycle performance and the useful life of improving electrode there is the cycle performance better than carbon negative pole.And lithium titanate material electromotive force is than the height of pure metal lithium, is difficult for producing lithium dendrite arm, for the safety that ensures lithium battery provides the foundation, is considered to thoroughly to solve the fail safe of lithium battery.Lithium titanate material and PC have good compatibility, can not cause lithium titanate material to peel off because large molecule embeds.But the easy inflatable of battery taking lithium titanate as negative pole main raw material(s), affects the cycle life of battery.
As the main electrolyte of electrolyte, be also electrolyte LiPF unique in most of electrolyte product
6, be the most stable electrolyte of current performance.But LiPF
6facile hydrolysis also can decompose and produce HF under the effect of traces of moisture.HF can destroy the SEI film of carbon material surface, makes battery produce inflatable, increases the irreversible capacity of battery, reduces the cycle life of battery.With respect to LiPF
6, LiBOB has the following advantages:
(1), insensitive to water, can be because the existence of water causes LiPF
6decompose and produce HF.
(2), can produce fine and close SEI film in negative terminal surface.
(3), high temperature performance is good.
(4), fail safe is good.
(5), cycle life is high.
Want the lithium-ion-power cell of excellent, need to consider its positive and negative pole material and electrolyte.
Summary of the invention
The object of the present invention is to provide a kind of nickle cobalt lithium manganate and lithium titanate system lithium ion battery.
The technical solution used in the present invention is:
A kind of nickle cobalt lithium manganate and lithium titanate system lithium ion battery, its positive electrode is by nickle cobalt lithium manganate 85～95 mass parts, adhesive 2～10 mass parts, conductive agent 2～10 mass parts; Its negative material is made up of lithium titanate 85～95 mass parts, adhesive 3～10 mass parts, conductive agent 3～10 mass parts; Its electrolyte contains electrolyte and organic solvent, and wherein electrolyte is LiPF
6or by LiPF
6with di-oxalate lithium borate composition, in organic solvent, contain quality percentage composition and be 20%～50% propene carbonate.
Preferably, the amount of substance concentration of electrolyte in electrolyte is 0.8～1.5mol/L.The quality percentage composition of LiBOB is 0～20% of electrolyte gross mass.
Preferably, the propene carbonate that organic solvent is 20%～50% by quality percentage composition, 20～40% diethyl carbonate and 20～40% methyl ethyl carbonate form.
Preferably, conductive agent is at least one in SP, superconduction carbon black, electrically conductive graphite, carbon nano-tube.
Preferably, adhesive is at least one in LA132, W811, PVDF.
The invention has the beneficial effects as follows:
Nickle cobalt lithium manganate of the present invention and lithium titanate system lithium ion battery, its electrolyte serviceability temperature wide ranges, chemical stability is good, has overcome and has used lithium titanate that the problem of inflatable easily occurs as electrode material, has improved its cycle life.Lithium ion battery of the present invention, safe, have extended cycle life.
Brief description of the drawings
Fig. 1 is the 1C discharge curve of battery of the present invention;
Fig. 2 is the curve of double curvature of battery of the present invention.
Embodiment
Lithium-ion-power cell provided by the invention comprises: positive pole, negative pole, barrier film, electrolyte, plastic casing, and use nickle cobalt lithium manganate as anodal main active substances, lithium titanate is as negative pole main active substances.
Positive and negative electrode material is used respectively to dissolution with solvents, and high speed dispersion becomes positive and negative electrode slurry, evenly coats afterwards on collector.In the present invention, collector is chosen as aluminium foil.Coating finishes through cutting, be laminated into battery core after baking, roll-in together with barrier film, and battery core is through entering shell, assembling, baking, enter the fluid injection of fluid injection operation after forming and capacity dividing become 20Ah battery.
A kind of nickle cobalt lithium manganate and lithium titanate system lithium ion battery, its positive electrode is by nickle cobalt lithium manganate 85～95 mass parts, adhesive 2～10 mass parts, conductive agent 2～10 mass parts; Its negative material is made up of lithium titanate 85～95 mass parts, adhesive 3～10 mass parts, conductive agent 3～10 mass parts; Its electrolyte contains electrolyte and organic solvent, and wherein electrolyte is LiPF
6or by LiPF
6with di-oxalate lithium borate composition, in organic solvent, contain quality percentage composition and be 20%～50% propene carbonate.Better, positive electrode is by nickle cobalt lithium manganate 89～94 mass parts, adhesive 3～5 mass parts, conductive agent 3～6 mass parts; Its negative material is made up of lithium titanate 85～92 mass parts, adhesive 3～8 mass parts, conductive agent 3～7 mass parts.
Preferably, the amount of substance concentration of electrolyte in electrolyte is 0.8～1.5mol/L.The quality percentage composition of LiBOB is 0～20% of electrolyte gross mass, is more preferred from 4%～10%.
Preferably, the propene carbonate that organic solvent is 20%～50% by quality percentage composition, 20～40% diethyl carbonate and 20～40% methyl ethyl carbonate form.
Preferably, conductive agent is at least one in SP, superconduction carbon black, electrically conductive graphite, carbon nano-tube.
Preferably, adhesive is at least one in LA132, W811, PVDF.
Below in conjunction with embodiment, further illustrate the present invention.
In following examples, if no special instructions, described percentage is mass percent.
Wherein electrolyte is LiPF
6or by LiPF
6form with di-oxalate lithium borate.
embodiment 1
A kind of nickle cobalt lithium manganate and lithium titanate system lithium ion battery
Its positive electrode is made up of nickle cobalt lithium manganate 90 mass parts, adhesive 5 mass parts, conductive agent 5 mass parts, and wherein, adhesive is LA132, and conductive agent is SP;
Its negative material is made up of lithium titanate 90 mass parts, adhesive 5 mass parts, conductive agent 5 mass parts, and wherein, adhesive is LA132, and conductive agent is electrically conductive graphite;
Its electrolyte contains electrolyte and solvent, and wherein electrolyte concentration is 1.0 mol/L, and di-oxalate lithium borate mass percentage content is 5%, and solvent is made up of PC, DEC and the EMC of equivalent.
A kind of nickle cobalt lithium manganate and lithium titanate system lithium ion battery
Its positive electrode is made up of nickle cobalt lithium manganate 89 mass parts, adhesive 5 mass parts, conductive agent 6 mass parts, and wherein, adhesive is W811, and conductive agent is superconduction carbon black;
Its negative material is made up of lithium titanate 91 mass parts, adhesive 5 mass parts, conductive agent 4 mass parts, and wherein, adhesive is LA132, and conductive agent is carbon nano-tube;
Its electrolyte contains electrolyte and solvent, and electrolyte concentration is 1.2 mol/L, and wherein di-oxalate lithium borate mass percentage content is 10%, and solvent is made up of 20% PC, 40% DEC and 40% EMC.
embodiment 3
A kind of nickle cobalt lithium manganate and lithium titanate system lithium ion battery
Its positive electrode is made up of nickle cobalt lithium manganate 92 mass parts, adhesive 4 mass parts, conductive agent 4 mass parts, and wherein, adhesive is W811, and conductive agent is made up of SP, superconduction carbon black, the electrically conductive graphite of equivalent;
Its negative material is made up of lithium titanate 85 mass parts, adhesive 8 mass parts, conductive agent 7 mass parts, and wherein, adhesive is LA132, and conductive agent is mixed and forms by the mass ratio of 3:1 by carbon nano-tube, SP;
Its electrolyte contains electrolyte and solvent, and wherein electrolyte is by LiPF
6with di-oxalate lithium borate composition, concentration is 0.8 mol/L, and wherein LiBOB mass percentage content is 4%.Solvent is made up of 40% PC, 20% DEC and 40% EMC.
embodiment 4
A kind of nickle cobalt lithium manganate and lithium titanate system lithium ion battery
Its positive electrode is made up of nickle cobalt lithium manganate 94 mass parts, adhesive 3 mass parts, conductive agent 3 mass parts, and wherein, adhesive is PVDF, and conductive agent is made up of superconduction carbon black, the electrically conductive graphite of equivalent;
Its negative material is made up of lithium titanate 92 mass parts, adhesive 5 mass parts, conductive agent 3 mass parts, and wherein, adhesive is LA132, and conductive agent is mixed and forms by the mass ratio of 2:3 by carbon nano-tube, superconduction carbon black;
Its electrolyte contains electrolyte and solvent, and wherein electrolyte is by LiPF
6with di-oxalate lithium borate composition, concentration is 1.2 mol/L, and wherein di-oxalate lithium borate mass percentage content is 6%.Solvent is made up of 20% PC, 40% DEC and 40% EMC.
Fig. 1 is the 1C discharge curve of the embodiment of the present invention 1 battery, and Fig. 2 is the curve of double curvature of the embodiment of the present invention 1 battery.As can be seen from the figure, battery of the present invention has little charge-discharge performance, long service life.
Claims (1)
1. nickle cobalt lithium manganate and a lithium titanate system lithium ion battery, its positive electrode is made up of nickle cobalt lithium manganate 90 mass parts, adhesive 5 mass parts, conductive agent 5 mass parts, and wherein, adhesive is LA132, and conductive agent is SP; Its negative material is made up of lithium titanate 90 mass parts, adhesive 5 mass parts, conductive agent 5 mass parts, and wherein, adhesive is LA132, and conductive agent is electrically conductive graphite; Its electrolyte contains electrolyte and organic solvent, and wherein electrolyte concentration is 1.0 mol/L, and electrolyte is by LiPF
6with di-oxalate lithium borate composition, the mass percent of di-oxalate lithium borate is 5% of electrolyte gross mass, organic solvent by etc. propene carbonate PC, diethyl carbonate DEC and the methyl ethyl carbonate EMC of mass percent form.
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| CN201110239541.6A CN102306830B (en) | 2011-08-20 | 2011-08-20 | Nickel-cobalt lithium manganate and lithium titanate system lithium ion battery with high-performance electrolyte solution |
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|---|---|---|---|
| CN201110239541.6A CN102306830B (en) | 2011-08-20 | 2011-08-20 | Nickel-cobalt lithium manganate and lithium titanate system lithium ion battery with high-performance electrolyte solution |
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| CN102306830A CN102306830A (en) | 2012-01-04 |
| CN102306830B true CN102306830B (en) | 2014-06-25 |
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| CN107271610A (en) * | 2017-06-16 | 2017-10-20 | 长沙新材料产业研究院有限公司 | A kind of method for being used to predict the remaining life cycle of LiMn2O4 lithium titanate battery |
| CN111129576A (en) * | 2019-12-20 | 2020-05-08 | 山东精工电子科技有限公司 | High-temperature-resistant long-cycle lithium ion battery |
| CN111540951A (en) * | 2020-05-12 | 2020-08-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Lithium ion battery high-voltage electrolyte for lithium titanate negative electrode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101388474A (en) * | 2008-11-07 | 2009-03-18 | 中南大学 | Lithium manganate cell |
| CN101447589A (en) * | 2007-11-27 | 2009-06-03 | 比亚迪股份有限公司 | Lithium ion battery nonaqueous electrolysing solution and lithium ion battery containing the same |
| CN101958428A (en) * | 2010-09-15 | 2011-01-26 | 东莞新能源科技有限公司 | Lithium ion secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101447589A (en) * | 2007-11-27 | 2009-06-03 | 比亚迪股份有限公司 | Lithium ion battery nonaqueous electrolysing solution and lithium ion battery containing the same |
| CN101388474A (en) * | 2008-11-07 | 2009-03-18 | 中南大学 | Lithium manganate cell |
| CN101958428A (en) * | 2010-09-15 | 2011-01-26 | 东莞新能源科技有限公司 | Lithium ion secondary battery |
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