CN103050732A - Lithium titanate-based chemical power supply - Google Patents
Lithium titanate-based chemical power supply Download PDFInfo
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- CN103050732A CN103050732A CN2012105577177A CN201210557717A CN103050732A CN 103050732 A CN103050732 A CN 103050732A CN 2012105577177 A CN2012105577177 A CN 2012105577177A CN 201210557717 A CN201210557717 A CN 201210557717A CN 103050732 A CN103050732 A CN 103050732A
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- lithium titanate
- chemical power
- lithium
- power source
- anodal
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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 lithium titanate-based chemical power supply which consists of an anode, a cathode, a diaphragm and an electrolyte and is characterized in that the anode and the cathode respectively consist of active substances and current collectors, wherein the cathode active substance is lithium titanate, the capacity of the anode active substance is excessive, and the capacity ratio of the anode active substance to the cathode active substance is between (1.1:1)-(4:1). The lithium titanate-based chemical power supply has the advantages of excellent large-magnification charging-discharging performance, long cycling life, high safety and good cycling performance, so that the chemical power supply has wider application field.
Description
Technical field
The present invention relates to field of chemical power source, relate to especially a kind of lithium titanate base chemical power source.
Background technology
Lithium titanate (Li
4Ti
5O
12) be a kind of novel lithium ion battery negative material, the characteristics of its maximum are exactly " zero strain ".Lattice constant and change in volume were all very little when so-called " zero strain " referred to its crystal in embedding or deviate from lithium ion.In charge and discharge cycles, this " zero strain " can be avoided owing to stretching back and forth of electrode material causes structural damage, thereby improved the cycle life of electrode, reduced the special capacity fade that circulation brings, also had extraordinary overcharging resisting, cross and put feature; So lithium titanate also is a kind of battery material of excellence and the negative material of hybrid super capacitor.Lithium titanate can have the life-span more than 30,000 times theoretically, but owing to be subjected to the restriction of positive electrode cycle life and electrolyte technology, the chemical power source device cycle life take lithium titanate as negative pole is well below 30000 times, and is the highest about 6000 times.
Carbon Materials negative electrode lithium ion chemical power source generally adopts the design of the excessive anodal limited capacity of negative pole, and this is because if negative pole limited capacity positive pole is excessive, anodal unnecessary lithium ion can be separated out in negative terminal surface, forms Li dendrite, causes the serious accidents such as short circuit.And lithium titanate anode, because embedding lithium current potential is higher, when positive pole is excessive, unnecessary lithium ion can not occur in the lithium titanate anode surface and separate out the formation Li dendrite, and anodal when excessive, device circulates at 100% depth of discharge (DOD), and lithium ion embeds the compound positive electrode and is in the circulation that is lower than 100%DOD, improves to a certain extent cycle life.
In addition, present lithium ion battery and the used electrolyte of lithium-ion capacitor, solvent mostly are greatly ethylene carbonate and linear carbonates forms, and solute is LiPF
6Or LiAsF
6, this kind electrolyte characteristics are technology maturation, be suitable for very much carbon back lithium ion battery and carbon back lithium-ion capacitor, but such electrolytic conductivity are lower, generally about 10mS/cm; Acetonitrile (CH
3CN) be intensive polar solvent, with the carbonates solvent phase than the conductivity that can improve electrolyte, CH
3CN successfully has been used for not producing the electrochemical system of solid electrolyte interface (SEI) film, and lithium titanate is as negative material, and the SEI film does not produce, and electrolyte can be used CH
3CN is as solvent; But because LiPF
6, LiAsF
6And LiBF
4At CH
3CN solubility is lower, generally below 2M, and LiNO
3At CH
3CN solubility is higher, and saturated concentration is 7M, can obtain higher conductivity; While LiNO
3Cost is lower, purifying is simple, insensitive to water, be used for doing solute, can reduce cost and the technological requirement of chemical power source.
And ultracapacitor (Supercapacitor) is a kind of model electrochemical energy storage device between traditional capacitor and battery.One is compared traditional capacitor, and ultracapacitor has higher energy density; Its two, compare battery, ultracapacitor has higher power density and better cycle life.
Summary of the invention
In order to overcome deficiency of the prior art, the present invention proposes a kind of lithium titanate base chemical power source, chemical power source with lithium titanate and the making of ultracapacitor internal mix, combine the advantage of battery and ultracapacitor, so that this chemical power source had both had high energy density, has again good large multiplying power discharging characteristic.
The present invention proposes a kind of lithium titanate base chemical power source, by positive pole, and negative pole, barrier film and electrolyte form, and it is characterized in that described positive pole and negative pole are comprised of active material and collector respectively; Wherein negative electrode active material is lithium titanate, and the positive active material capacity is excessive, and the ratio of the capacity of anodal and negative electrode active material is between 1.1:1 ~ 4:1.
Wherein, the active material of described positive pole is that lithium ion embeds compound, or lithium ion embeds compound and double electric layer capacitor material blends.
Wherein, described electrolyte is by solute and solvent composition, and solvent is acetonitrile (CH
3CN), solute is lithium nitrate (LiNO
3), solute concentration is 0.8～6.0M, preferred concentration is 1.0～3.0M.
Wherein, it is LiMn2O4 that described lithium ion embeds compound, one of nickle cobalt lithium manganate or LiFePO4.
Wherein, described double electric layer capacitor material is one or more in active carbon, Graphene, carbon nanotube and the charcoal-aero gel.
Wherein, described barrier film comprises polyethene microporous membrane, microporous polypropylene membrane, composite membrane, inorganic ceramic membrane or paper barrier film.
Lithium titanate base chemical power source of the present invention, not only the high rate charge-discharge performance is excellent, and has extended cycle life, and has high safety and good cycle performance, so that this kind chemical power source has wider application.
Embodiment
Describe technical scheme of the present invention in detail below in conjunction with specific embodiment.
The manufacture method of embodiment 1-12 is as follows in the table 1:
The making of positive plate: with nickle cobalt lithium manganate (LiNi
1/3Co
1/3Mn
1/3O
2) separately as active material, or with nickle cobalt lithium manganate (LiNi
1/3Co
1/3Mn
1/3O
2) and active carbon mix according to a certain percentage, then the furnishing slurry is coated on the collector, drying (110～120 ℃), roll, cut-parts, 24h vacuumize (120～130 ℃) are made into positive plate.
The making of negative plate: be active material furnishing slurry with lithium titanate, then be coated on the collector, drying (110～120 ℃), roll, cut-parts, 24h vacuumize (120～130 ℃) are made into negative plate.
Selecting cellulose paper is barrier film, injects at last 3M LiNO
3/ CH
3Then CN changes into and performance test this chemical power source.
The manufacture method of embodiment 13-22 is as follows in the table 2:
Select both positive and negative polarity that table 1 obtains than preferred embodiment, i.e. nickle cobalt lithium manganate (LiNi in the anode pole piece
1/3Co
1/3Mn
1/3O
2) being 50 parts with active carbon, Capacity Ratio anodal and negative pole is 2, then injects the electrolyte of different formulations and the electrolyte of variable concentrations.Be assembled into the chemical power source of 3Ah.Then this chemical power source is changed into and performance test.
Work system:
Life test: power supply with the current charges of 30A to 2.7V, 2.7V constant voltage 5min, 30A is discharged to 1.8V, circulates after 20000 times the calculated capacity conservation rate.
Embodiment 1
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, anodal face amount is 21Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 1.05.
Embodiment 2
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, anodal face amount is 22Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 1.1.
Embodiment 3
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, anodal face amount is 30Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 1.5.
Embodiment 4
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, anodal face amount is 40Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 2.0.
Embodiment 5
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, anodal face amount is 60Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 3.0.
Embodiment 6
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, anodal face amount is 70Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 3.5.
(the anodal face amount of this example is too high, can not be coated with).
Embodiment 7
Anodal: LiNi
1/3Co
1/3Mn
1/3O
250 parts, 50 parts of active carbons, anodal face amount 21Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 1..05.
Embodiment 8
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 22Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 1.1.
Embodiment 9
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 30Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 1.5.
Embodiment 10
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 40Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 2.0.
Embodiment 11
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 50Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 2.5.
Embodiment 12
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 60Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 3.
(the anodal face amount of this example is too high, can not be coated with).
Embodiment 13
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 40Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 2.0.
Concentration of electrolyte is 0.6M.
Embodiment 14
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 40Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 2.0.
Concentration of electrolyte is 0.8M.
Embodiment 15
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 40Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 2.0.
Concentration of electrolyte is 1.0M.
Embodiment 16
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 40Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 2.0.
Concentration of electrolyte is 1.5M.
Embodiment 17
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 40Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 2.0.
Concentration of electrolyte is 2.0M.
Embodiment 18
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 40Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 2.0.
Concentration of electrolyte is 3.0M.
Embodiment 19
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 40Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 2.0.
Concentration of electrolyte is 4.0M.
Embodiment 20
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 40Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 2.0.
Concentration of electrolyte is 5.0M.
Embodiment 21
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 40Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 2.0.
Concentration of electrolyte is 6.0M.
Embodiment 22
Anodal: LiNi
1/3Co
1/3Mn
1/3O
2, 50 parts of active carbons, anodal face amount is 40Ah/m
2
Negative pole: lithium titanate, negative pole face amount is 20Ah/m
2
Positive pole and capacity of negative plates ratio: 2.0.
Concentration of electrolyte is 6.5M.
Table 1 is the chemical power source electrical property table of comparisons of different proportionings
Table 2 is the chemical power source electrical property table of comparisons of different electrolytes concentration
As can be seen from Table 1, no matter simple anode material for lithium-ion batteries is as positive active material in the situation that can be coated with, or anode material for lithium-ion batteries and active carbon are compound as active material, cycle life all raises and raises along with both positive and negative polarity capacity ratio, and specific energy and specific power all slightly reduce along with the rising of both positive and negative polarity proportioning.Under identical proportioning, simple anode material for lithium-ion batteries is higher than anode material for lithium-ion batteries and the compound device as positive active material of active carbon as the device specific energy of positive active material, but specific power and cycle life are not as good as the latter.We can draw table 1, and the ratio of the both positive and negative polarity capacity of the device in the invention should be greater than 1.1.
Concentration of electrolyte is little on the specific energy impact of device as can be seen from Table 2, but larger on specific power and cycle life impact.Cross to exceed and low be unfavorable for that all specific power and cycle life, its suitable concn are 0.8～6.0M, consider that its preferred concentration of cost is 1.0～3.0M.
Described in this specification is preferred embodiment of the present invention, and above embodiment is only in order to illustrate technical scheme of the present invention but not limitation of the present invention.All those skilled in the art all should be within the scope of the present invention under this invention's idea by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (6)
1. lithium titanate base chemical power source, by positive pole, negative pole, barrier film and electrolyte form, and it is characterized in that described positive pole and negative pole are comprised of active material and collector respectively; Wherein negative electrode active material is lithium titanate, and the positive active material capacity is excessive, and the ratio of the capacity of anodal and negative electrode active material is between 1.1:1 ~ 4:1.
2. lithium titanate base chemical power source as claimed in claim 1, the active material that it is characterized in that described positive pole are that lithium ion embeds compound, or lithium ion embeds compound and double electric layer capacitor material blends.
3. lithium titanate base chemical power source as claimed in claim 1 is characterized in that described electrolyte by solute and solvent composition, and solvent is acetonitrile (CH
3CN), solute is lithium nitrate (LiNO
3), solute concentration is 0.8～6.0M, preferred concentration is 1.0～3.0M.
4. lithium titanate base chemical power source as claimed in claim 2 is characterized in that it is LiMn2O4 that described lithium ion embeds compound, one of nickle cobalt lithium manganate or LiFePO4.
5. lithium titanate base chemical power source as claimed in claim 2 is characterized in that described double electric layer capacitor material is one or more in active carbon, Graphene, carbon nanotube and the charcoal-aero gel.
6. lithium titanate base chemical power source as claimed in claim 1 is characterized in that described barrier film comprises polyethene microporous membrane, microporous polypropylene membrane, composite membrane, inorganic ceramic membrane or paper barrier film.
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Cited By (7)
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|---|---|---|---|---|
| CN103746139A (en) * | 2013-12-10 | 2014-04-23 | 宁波维科电池股份有限公司 | Lithium ion power battery with good safety performances |
| CN104332656A (en) * | 2013-07-22 | 2015-02-04 | 浙江万向亿能动力电池有限公司 | Method for solving expanding of lithium ion battery using lithium titanate as negative electrode |
| CN104466230A (en) * | 2013-09-13 | 2015-03-25 | 浙江万向亿能动力电池有限公司 | Lithium titanate battery based on lithium-enriched manganese anode and charging method thereof |
| CN104577044A (en) * | 2014-11-18 | 2015-04-29 | 深圳市金润能源材料有限公司 | Lithium titanate battery and preparation method thereof |
| CN105322221A (en) * | 2014-07-31 | 2016-02-10 | 株式会社东芝 | Nonaqueous electrolyte battery and battery pack |
| CN105810997A (en) * | 2014-12-31 | 2016-07-27 | 龙能科技（苏州）有限公司 | Lithium ion battery electrolyte solution and preparation method thereof, and lithium ion battery |
| WO2023070872A1 (en) * | 2021-10-29 | 2023-05-04 | 海南大学 | Negative-electrode-free zinc ion hybrid capacitor and preparation method therefor |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104332656A (en) * | 2013-07-22 | 2015-02-04 | 浙江万向亿能动力电池有限公司 | Method for solving expanding of lithium ion battery using lithium titanate as negative electrode |
| CN104466230A (en) * | 2013-09-13 | 2015-03-25 | 浙江万向亿能动力电池有限公司 | Lithium titanate battery based on lithium-enriched manganese anode and charging method thereof |
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| CN105322221A (en) * | 2014-07-31 | 2016-02-10 | 株式会社东芝 | Nonaqueous electrolyte battery and battery pack |
| CN105322221B (en) * | 2014-07-31 | 2019-03-29 | 株式会社东芝 | The manufacturing method and battery pack of nonaqueous electrolyte battery, nonaqueous electrolyte battery |
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| CN104577044A (en) * | 2014-11-18 | 2015-04-29 | 深圳市金润能源材料有限公司 | Lithium titanate battery and preparation method thereof |
| CN105810997A (en) * | 2014-12-31 | 2016-07-27 | 龙能科技（苏州）有限公司 | Lithium ion battery electrolyte solution and preparation method thereof, and lithium ion battery |
| WO2023070872A1 (en) * | 2021-10-29 | 2023-05-04 | 海南大学 | Negative-electrode-free zinc ion hybrid capacitor and preparation method therefor |
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| CN103050732B (en) | 2015-04-29 |
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Denomination of invention: A Lithium Titanate Based Chemical Power Supply Effective date of registration: 20230426 Granted publication date: 20150429 Pledgee: China Minsheng Banking Corp Shanghai branch Pledgor: SHANGHAI AOWEI TECHNOLOGY DEVELOPMENT Co.,Ltd. Registration number: Y2023310000145 |