CN106299329B - A kind of lithium-ion-power cell of high capacity titanium system's negative electrode material and its composition - Google Patents
A kind of lithium-ion-power cell of high capacity titanium system's negative electrode material and its composition Download PDFInfo
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- CN106299329B CN106299329B CN201510256170.0A CN201510256170A CN106299329B CN 106299329 B CN106299329 B CN 106299329B CN 201510256170 A CN201510256170 A CN 201510256170A CN 106299329 B CN106299329 B CN 106299329B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to the lithium-ion-power cells a kind of high capacity titanium system's negative electrode material and be made of the material.The active material of high capacity titanium system cathode includes lithium titanate (Li4Ti5O12) material and the modified niobium titanium oxide (TiNb of another high capacity2‑xZrxO7- yC, 0 x≤0.1 <；0 < y≤0.1) material, wherein modified niobium titanium oxide material accounts for the 20%~80% of the negative electrode active material total amount.The lithium ion battery prepared using high capacity titanium system's negative electrode material of the invention, with higher-security, compared with the battery of existing lithium titanate anode, further improve the capacity and energy density of battery, to improve the course continuation mileage of titanium system cathode power battery, it is played in the application advantage of electric automobiles.
Description
Technical field
The invention belongs to technical field of lithium ion, are related to a kind of high capacity titanium system negative electrode lithium ion power battery.
Background technique
In recent years, with the support energetically of national and local governments, the demand of electric automobile market is constantly increasing.Electricity
Pond safety, cruising ability are to determine the key factor of power battery development.
To meet requirement of the lithium-ion-power cell to security performance, people begin to focus on the negative electrode material other than graphite.
Lithium titanate (Li4Ti5O12) material due to intercalation potential height and zero strain effect the features such as, have it during fast charging and discharging
There are good cyclical stability and superior safety, it is considered to be the ideal negative electrode material of alternative graphite.But lithium titanate
Specific capacity it is lower and higher to lithium current potential, cause its energy density lower so that lithium titanate battery be applied to electric automobiles
When, course continuation mileage cannot fully meet consumer demand.
2011 Goodenough (chem.Mater.2011,23,2027-2029) niobium titanium oxide is used for lithium for the first time
The negative electrode material of ion battery, this niobium titanium oxide and lithium titanate have similar removal lithium embedded current potential, same to have preferably
Safety, and have higher compacted density and specific capacity compared to the lithium titanate material material, therefore full battery is with higher
Energy density.Chinese patent application 201110336136.6 of Toshiba's application disclose niobium titanium oxide and can be used as battery-active
Substance, battery energy density with higher.However niobium titanium oxide material in cyclic process material structure crystal form variation compared with
Cause its cycle performance and high rate performance poor greatly, these disadvantages limit its practical application.To improve niobium titanium oxide material
Circulation and high rate performance, applicant have applied for that Chinese patent application 201410317846.8 disclose and are mixed with type niobium titanyl
The preparation method of compound, however used separately as negative electrode active material and be still difficult to meet electric car for service life and power spy
The demand of property.
The present invention utilizes the reapective features of two kinds of materials of lithium titanate material and niobium titanium oxide by many experiments discovery, presses
Certain proportion is used in mixed way, and as composite negative pole material, may be implemented the height of lithium titanate long-life and modified niobium titanium oxide
Capacity characteristic carries out advantage combination, performance complement, to be prepared into the characteristic of high capacity titanium system negative electrode lithium ion power battery.Its
Middle modified niobium titanium oxide material is based on the above-mentioned patent application of our company and is prepared.Thus obtained high capacity composite titanium system is negative
Pole battery had both improved existing titanium system cathode (lithium titanate) battery on the basis of maintaining the higher-security of titanium system cathode
Capacity and energy density to improve the course continuation mileage of titanium system cathode power battery, while also having preferable cycle performance,
Make titanium system cathode power battery in electric automobiles with more application advantage.
Summary of the invention
The invention discloses a kind of preparation methods of high capacity titanium system negative electrode lithium ion power battery.
The present invention is realized by the following scheme: a kind of high capacity titanium system negative electrode lithium ion power battery, the cathode include
Lithium titanate (Li4Ti5O12) and the modified two kinds of active materials of niobium titanium oxide of high capacity.The modified niobium titanium oxide has following
General formula: TiNb2-xZrxO7- yC, wherein 0 < x≤0.1,0 < y≤0.1, the modified niobium titanium oxide account for two kinds of negative electrode active materials
Expect the 20%~80% of gross mass.Wherein, the embodiment in following specific embodiments can be seen that, niobium titanium oxide and lithium titanate
When mixed proportion is 5:5 (50%) (embodiment two, four, five), comprehensive performance is optimal, is negative electrode material comprehensive performance of the present invention
Optimal proportion.But according to the specific requirement to service life and course continuation mileage, two kinds of materials can be selected within the scope of the invention not
Titanium system cathode is prepared with mixed proportion.
The preparation method of cathode of the present invention, including the following steps:
1, more mixed than carrying out dry powder by certain mass by negative electrode active material lithium titanate material and modified niobium titanium oxide material
It closes；
2, by mixed negative electrode active material (lithium titanate material and modified niobium titanium oxide material), conductive agent, bonding
Agent is dissolved in nmp solvent by certain mass ratio, and uniform negative electrode slurry is stirred into double planetary mixer；
3, on a current collector by the coating of manufactured slurry, the cathode of lithium ion battery is made in drying and roll-in.
The modified niobium titanium oxide material accounts for the 20% of the negative electrode active material gross mass in some embodiments
~80%；The conductive agent includes one of conductive black, acetylene black, carbon fiber and carbon nanotube or a variety of, preferably
Conductive black；The binder is polyvinylidene fluoride；The negative electrode active material material, conductive agent, binder mass ratio
Example is preferably 90:5:5.
A kind of high capacity titanium system of the present invention negative electrode lithium ion power battery includes anode, cathode and electrolyte.It is described
Just extremely one of cobalt acid lithium, LiMn2O4 and nickel-cobalt lithium manganate material or a variety of, preferably cobalt acid lithium；High capacity titanium system
Negative electrode lithium ion power battery is preferably laminated flexible-packaging lithium ion battery.
High capacity titanium of the present invention system negative electrode lithium ion power battery, has the following characteristics that
1, lithium titanate material " zero strain " characteristic makes it have excellent stable cycle performance；The spinelle of three-dimensional channel
Structure and characteristics of nanoparticles determine its higher ionic conductivity；
2, Nb in niobium titanium oxide5+/Nb4+And Nb4+/Nb3+Oxidation-reduction potential between 1~3V, can be realized 2
Electronics transfer, therefore there is higher theoretical capacity, currently preferred modified niobium titanium oxide TiNb1.98Zr0.02O7-0.1C
Actual specific capacity is 301mAh/g, and the actual specific capacity compared to lithium titanate 165mAh/g is higher, meanwhile, niobium Titanium oxide particles compared with
Lithium titanate is big, has higher compacted density, therefore have higher energy density；
3, by the element doping and material with carbon-coated surface to titanium oxide, can further improve its circulation and it is forthright again
Energy.
4, lithium titanate and modified two kinds of materials of niobium titanium oxide are mixed in a certain ratio used as cathode, the height of preparation
Capacity power battery keeps the high security of titanium system cathode, further increases the energy of traditional titanium system cathode (lithium titanate) battery
Density, while there is preferable cycle performance, it is applied to electric automobiles, the advantage with excellent combination property.
Detailed description of the invention
Fig. 1 is the button cell specific capacity of titanium system negative electrode material prepared by comparative example one, two and embodiment one, two, three.
Fig. 2 is cathode button electricity charging and discharging curve prepared by comparative example and embodiment one, two, three.
25Ah battery charging and discharging curve prepared by Fig. 3 comparative example and embodiment one, two, three.
Fig. 4 is 60 DEG C of circulation correlation curves of 25Ah battery prepared by comparative example and embodiment.
Fig. 5 is the XRD diagram of titanium system cathode prepared by embodiment two.
Specific embodiment
The present invention is elaborated below with reference to embodiment, the present invention is not limited only to the embodiment.
Embodiment one
By active material TiNb1.98Zr0.02O7- 0.1C material and Li4Ti5O12Material carries out dry powder according to 2:8 mass ratio and mixes
30min is closed, is that 90:5:5 weighs powder according to active material, conductive black, PVDF mass ratio, using NMP as solvent, in double-planet
5h is sufficiently stirred in blender to be uniformly coated on aluminium foil at uniform sizing material, then by slurry, 100 DEG C baking 12 hours after roll-in
Negative electrode tab is made.
Positive plate is made using cobalt acid lithium as active material in anode according to the method described above.Use Celgard diaphragm, electrolyte
For 1.0mol/L LiPF6(PC:DMC=1:1), flexible package 25Ah lithium-ion-power cell is prepared.
Embodiment two
Negative electrode active material TiNb in the present embodiment1.98Zr0.02O7- 0.1C and Li4Ti5O12Mass ratio is 5:5, other mistakes
Journey is the same as embodiment one.
Embodiment three
Negative electrode active material TiNb in the present embodiment1.98Zr0.02O7- 0.1C and Li4Ti5O12Mass ratio is 8:2, other mistakes
Journey is the same as embodiment one.
Example IV
Negative electrode active material is TiNb in the present embodiment1.98Zr0.02O7- 0.05C and Li4Ti5O12Mass ratio is 5:5, other
Process is the same as embodiment one.
Embodiment five
Negative electrode active material is TiNb in the present embodiment1.98Zr0.05O7- 0.1C and Li4Ti5O12Mass ratio is 5:5, other
Process is the same as embodiment one.
Comparative example one
Negative electrode active material is Li in the present embodiment4Ti5O12, other processes are the same as embodiment one.
Comparative example two
Negative electrode active material is TiNb in the present embodiment1.98Zr0.02O7- 0.1C, other processes are the same as embodiment one.
Comparative example and comparative example are it is found that TiNb1.98Zr0.02O7- 0.1C and Li4Ti5O12After mixing, as the former contains
Amount increases, and the specific capacity of material increases, but irreversible capacity also increased for the first time simultaneously.By the specific volume in charge and discharge process
It is not each component capacity and proportion that amount-voltage curve, which can be seen that and mix the specific capacity of negative electrode material in this experiment,
Simple computation value, this show mix cathode in two kinds of materials be not individually to work, but deposit in charge and discharge process
In synergistic effect, influence each other.
The 25Ah lithium-ion-power cell performance made in above-described embodiment is compared, with high capacity niobium titanyl
The energy density of the increase of object content, designed 25Ah battery is also increasing；But under 60 DEG C of cycle performances of battery slightly have simultaneously
It drops (being detailed in the following table 1).As can be seen that niobium titanium oxide and lithium titanate mixed proportion (are implemented when being 5:5 from the embodiment of the present invention
Example two, four), comprehensive performance is optimal, but user can select two kinds of materials not according to the specific requirement to service life and course continuation mileage
Titanium system cathode is prepared with mixed proportion.
The properties of product table of comparisons of table 1 embodiment 1-5 and comparative example 1-2
Claims (6)
1. a kind of high capacity titanium system negative electrode material, which is characterized in that the negative electrode material includes lithium titanate and modified niobium titanyl
Two kinds of active materials of object, the modified niobium titanium oxide have following general formula:
TiNb2-xZrxO7- yC, wherein 0 < x≤0.1,0 < y≤0.1.
2. negative electrode material according to claim 1, which is characterized in that the modified niobium titanium oxide accounts for two kinds of active materials
The 20%~80% of gross mass.
3. a kind of high capacity titanium system cathode comprising negative electrode material of any of claims 1 or 2, which is characterized in that the cathode
Include the negative electrode material, conductive agent and binder, wherein the conductive agent includes that conductive black, carbon nano-fiber or carbon are received
One of mitron is a variety of, and the binder is polyvinylidene fluoride.
4. the high capacity titanium system cathode of negative electrode material according to claim 3, which is characterized in that the conductive black is second
Acetylene black.
5. a kind of high capacity titanium system negative electrode lithium ion power battery, including anode, cathode and electrolyte, which is characterized in that described
Cathode includes negative electrode material of any of claims 1 or 2, and the anode includes cobalt acid lithium, LiMn2O4 or nickel-cobalt lithium manganate material
One of or various active material.
6. a kind of high capacity titanium system negative electrode lithium ion power battery, including anode, cathode according to claim 3 or 4 and
Electrolyte, which is characterized in that the anode includes one of cobalt acid lithium, LiMn2O4 or nickel-cobalt lithium manganate material or various active
Material.
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| CN108284753A (en) * | 2017-01-08 | 2018-07-17 | 谭武 | Automatic vehicle principle and methods for using them |
| CN109004219A (en) * | 2017-06-07 | 2018-12-14 | 银隆新能源股份有限公司 | A kind of lithium ion battery comprising rare earth modified barium titanium composite oxide |
| WO2019187131A1 (en) | 2018-03-30 | 2019-10-03 | 株式会社 東芝 | Electrode group, battery, and battery pack |
| JP7155085B2 (en) * | 2019-09-13 | 2022-10-18 | 株式会社東芝 | Electrodes, secondary batteries, battery packs and vehicles |
| GB202013576D0 (en) * | 2020-08-28 | 2020-10-14 | Echion Tech Limited | Active electrode material |
| GB201915151D0 (en) * | 2019-10-18 | 2019-12-04 | Echion Tech Limited | Li/Na-ion battery anode materials |
| BR122023000464B1 (en) | 2020-06-03 | 2023-12-12 | Echion Technologies Limited | ELECTRODE COMPRISING ACTIVE ELECTRODE MATERIAL AND ELECTROCHEMICAL DEVICE |
| JP7331873B2 (en) * | 2021-01-28 | 2023-08-23 | トヨタ自動車株式会社 | All-solid battery |
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| CN103081187A (en) * | 2010-07-30 | 2013-05-01 | 德州系统大学董事会 | Niobium oxide compositions and methods for using same |
| CN104282899A (en) * | 2013-07-08 | 2015-01-14 | 株式会社东芝 | Active material, nonaqueous electrolyte battery, and battery pack |
| CN105990575A (en) * | 2015-03-19 | 2016-10-05 | 株式会社东芝 | Electrode, nonaqueous electrolyte battery, and battery pack |
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| CN1941459A (en) * | 2005-09-29 | 2007-04-04 | 株式会社东芝 | Nonaqueous electrolyte battery, battery pack and vehicle |
| CN103081187A (en) * | 2010-07-30 | 2013-05-01 | 德州系统大学董事会 | Niobium oxide compositions and methods for using same |
| CN104282899A (en) * | 2013-07-08 | 2015-01-14 | 株式会社东芝 | Active material, nonaqueous electrolyte battery, and battery pack |
| CN105990575A (en) * | 2015-03-19 | 2016-10-05 | 株式会社东芝 | Electrode, nonaqueous electrolyte battery, and battery pack |
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