CN106299329A - A kind of high power capacity titanium system's negative material and the lithium-ion-power cell of composition thereof - Google Patents
A kind of high power capacity titanium system's negative material and the lithium-ion-power cell of composition thereof Download PDFInfo
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- CN106299329A CN106299329A CN201510256170.0A CN201510256170A CN106299329A CN 106299329 A CN106299329 A CN 106299329A CN 201510256170 A CN201510256170 A CN 201510256170A CN 106299329 A CN106299329 A CN 106299329A
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- negative
- high power
- power capacity
- lithium
- titanium system
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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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- 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 present invention relates to a kind of high power capacity titanium system's negative material and the lithium-ion-power cell being made up of this material.The active substance of described high power capacity titanium system negative pole comprises lithium titanate (Li4Ti5O12) material and another kind of high power capacity modification niobium titanium oxide (TiNb2-xZrxO7-yC, 0 ＜ x≤0.1；0 < y≤0.1) material, wherein modified niobium titanium oxide material accounts for the 20%～80% of described negative electrode active material total amount.Use lithium ion battery prepared by the high power capacity titanium system negative material of the present invention, there is higher-security, compared with the battery of existing lithium titanate anode, further improve capacity and the energy density of battery, thus improve the course continuation mileage of titanium system negative pole electrokinetic cell, play its application advantage in electric automobiles.
Description
Technical field
The invention belongs to technical field of lithium ion, relate to a kind of high power capacity titanium system negative electrode lithium ion power current
Pond.
Background technology
In recent years, along with country and the support energetically of local government, the demand of electric automobile market is constantly
Increase.Battery security, flying power are the key factors determining electrokinetic cell development.
For meeting the lithium-ion-power cell requirement to security performance, people begin to focus on the negative pole beyond graphite
Material.Lithium titanate (Li4Ti5O12) material is owing to intercalation potential is high and the feature such as zero strain effect so that it is soon
Speed charge and discharge process have good cyclical stability and superior safety it is considered to be alternative graphite
Preferable negative material.But the specific capacity of lithium titanate is relatively low and higher to lithium current potential, cause its energy density
Relatively low so that when lithium titanate battery is applied to electric automobiles, course continuation mileage can not fully meet consumer
Demand.
2011 Goodenough (chem.Mater.2011,23,2027-2029) first by niobium titanium oxide use
In the negative material of lithium ion battery, this niobium titanium oxide and lithium titanate have close removal lithium embedded current potential,
There is preferable safety equally, and compare this material of lithium titanate material and have higher compacted density and specific volume
Amount, therefore full battery has higher energy density.The Chinese patent application 201110336136.6 of Toshiba's application
Number disclosing niobium titanium oxide can be as cell active materials, and battery has higher energy density.But niobium
Titanium oxide material material structure crystal formation in cyclic process changes greatly and causes its cycle performance and high rate performance
Poor, these shortcomings limit its actual application.For improving the circulation of niobium titanium oxide material and high rate performance,
Applicant has applied for that Chinese patent application 201410317846.8 discloses and has been mixed with type niobium titanium oxide
Preparation method, but use separately as negative active core-shell material and be still difficult to meet electric automobile for life-span and merit
The demand of rate characteristic.
The present invention finds to utilize the respective spy of lithium titanate material and niobium titanium oxide bi-material through great many of experiments
Point, is used in mixed way by a certain percentage, as composite negative pole material, it is possible to achieve by the lithium titanate long-life with change
The high capacity characteristics of property niobium titanium oxide carries out advantage combination, performance complement, thus is prepared as high power capacity titanium system
The characteristic of negative electrode lithium ion electrokinetic cell.Wherein modified niobium titanium oxide material is based on our company's above-mentioned patent Shen
Please be prepared.Thus obtained high power capacity composite titanium system negative battery is at the relatively Gao An maintaining titanium system negative pole
On the basis of full property, both improve capacity and the energy density of existing titanium system negative pole (lithium titanate) battery, from
And improve the course continuation mileage of titanium system negative pole electrokinetic cell, also there is preferable cycle performance simultaneously, make titanium system
Negative pole electrokinetic cell has more application advantage in electric automobiles.
Summary of the invention
The invention discloses the preparation method of a kind of high power capacity titanium system negative electrode lithium ion electrokinetic cell.
The present invention is realized by below scheme: a kind of high power capacity titanium system negative electrode lithium ion electrokinetic cell, described negative pole
Comprise lithium titanate (Li4Ti5O12) and high power capacity two kinds of active materials of modification niobium titanium oxide.Described modified niobium titanium
Oxide has below general formula: TiNb2-xZrxO7-yC, wherein, 0 ＜ x≤0.1,0 < y≤0.1, described modification
Niobium titanium oxide accounts for the 20%～80% of two kinds of negative active core-shell material gross masses.Wherein, detailed description below
In embodiment can be seen that, when niobium titanium oxide and lithium titanate mixed proportion are 5:5 (50%) (embodiment two,
Four, five), combination property is optimum, for the optimal proportion of negative material combination property of the present invention.But according to the longevity
Life and the specific requirement of course continuation mileage, can select the different mixing proportion of bi-material within the scope of the invention
Prepare titanium system negative pole.
The preparation method of negative pole of the present invention, comprises the following steps:
1, by negative electrode active material lithium titanate material and modified niobium titanium oxide material, carry out by certain mass ratio
Dry powder blend；
2, by mixed negative electrode active material (lithium titanate material and modified niobium titanium oxide material), conductive agent,
Binding agent is dissolved in nmp solvent by certain mass ratio, and in double planetary mixer, stirring is mixed into uniform negative
Pole slurry；
3, being coated on a current collector by the slurry made, the negative pole of lithium ion battery is made in drying and roll-in.
The most described modified niobium titanium oxide material accounts for described negative active core-shell material gross mass
20%～80%；Described conductive agent comprises the one in conductive black, acetylene black, carbon fiber and CNT
Or multiple, preferably conductive black；Described binding agent is polyvinylidene fluoride；Described negative electrode active material material
Material, conductive agent, the mass ratio of binding agent are preferably 90:5:5.
A kind of high power capacity of the present invention titanium system negative electrode lithium ion electrokinetic cell, comprises positive pole, negative pole and electrolyte.
One or more in described the most extremely cobalt acid lithium, LiMn2O4 and nickel-cobalt lithium manganate material, preferably cobalt acid lithium；
Described high power capacity titanium system negative electrode lithium ion electrokinetic cell is preferably laminated flexible-packaging lithium ion battery.
High power capacity of the present invention titanium system negative electrode lithium ion electrokinetic cell, has the following characteristics that
1, lithium titanate material " zero strain " characteristic so that it is there is excellent stable cycle performance；Three-dimensional channel
Spinel 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, energy
Enough realize 2 electron transfers, therefore there is higher theoretical capacity, currently preferred modified niobium titanyl
Thing TiNb1.98Zr0.02O7-0.1C actual specific capacity is 301mAh/g, compares the reality of lithium titanate 165mAh/g
Specific capacity is higher, and meanwhile, niobium Titanium oxide particles is big compared with lithium titanate, has higher compacted density, therefore
There is higher energy density；
3, by the element doping of titanium oxide and material with carbon-coated surface, its circulation and again can be improved further
Rate performance.
4, lithium titanate is used in mixed way as negative pole, system by a certain percentage with modified niobium titanium oxide bi-material
Standby high power capacity electrokinetic cell, keeps the high security of titanium system negative pole, improves tradition titanium system negative pole (titanium further
Acid lithium) energy density of battery, there is preferable cycle performance simultaneously, be applied to electric automobiles, have
The advantage of excellent combination property.
Accompanying drawing explanation
Fig. 1 is the button cell ratio of titanium system negative material prepared by comparative example one, two and embodiment one, two, three
Capacity.
Fig. 2 is negative pole 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 that 60 DEG C of 25Ah battery prepared by comparative example and embodiment circulates correlation curve.
Fig. 5 is the XRD figure of titanium system negative pole prepared by embodiment two.
Detailed description of the invention
Elaborating the present invention below in conjunction with embodiment, the present invention is not limited only to described embodiment.
Embodiment one
By active substance TiNb1.98Zr0.02O7-0.1C material and Li4Ti5O12Material is carried out according to 2:8 mass ratio
Dry powder blend 30min, is that 90:5:5 weighs powder according to active substance, conductive black, PVDF mass ratio
Material, with NMP as solvent, is sufficiently stirred for 5h uniformly slurry in double planetary mixer, then slurry is equal
Even is coated on aluminium foil, and 12 hours back roller of 100 DEG C of bakings are pressed into negative plate.
Positive pole, with cobalt acid lithium as active substance, makes positive plate according to the method described above.Use Celgard barrier film,
Electrolyte is 1.0mol/L LiPF6(PC:DMC=1:1), preparation flexible package 25Ah lithium-ion-power cell.
Embodiment two
Negative electrode active material TiNb in the present embodiment1.98Zr0.02O7-0.1C and Li4Ti5O12Mass ratio is 5:5,
Other process is with embodiment one.
Embodiment three
Negative electrode active material TiNb in the present embodiment1.98Zr0.02O7-0.1C and Li4Ti5O12Mass ratio is 8:2,
Other process is with embodiment one.
Embodiment four
In the present embodiment, negative electrode active material is TiNb1.98Zr0.02O7-0.05C and Li4Ti5O12Mass ratio is
5:5, other process is with embodiment one.
Embodiment five
In the present embodiment, negative electrode active material is TiNb1.98Zr0.05O7-0.1C and Li4Ti5O12Mass ratio is 5:5,
Other process is with embodiment one.
Comparative example one
In the present embodiment, negative electrode active material is Li4Ti5O12, other process is with embodiment one.
Comparative example two
In the present embodiment, negative electrode active material is TiNb1.98Zr0.02O7-0.1C, other process is with embodiment one.
Comparative example understands with comparative example, TiNb1.98Zr0.02O7-0.1C and Li4Ti5O12After mixing, along with
The former increases by content, and the specific capacity of material increases, but irreversible capacity also increased first.By filling
Specific capacity-voltage curve in discharge process is it can be seen that mix the specific capacity of negative material in this experiment also
Not being the simple computation value of each component capacity and proportion, this shows that the bi-material mixed in negative pole is filling
Discharge process is not individually work, but there is cooperative effect, influence each other.
The 25Ah lithium-ion-power cell performance made in above-described embodiment is contrasted, along with high power capacity niobium
The increase of titanium oxide content, the energy density of designed 25Ah battery is also increasing；But simultaneously battery
60 DEG C of cycle performances are declined slightly (referring to table 1 below).It can be seen that niobium titanyl from the embodiment of the present invention
When thing and lithium titanate mixed proportion are 5:5 (embodiment two, four), combination property is optimum, but user can basis
To life-span and the specific requirement of course continuation mileage, the different mixing proportion of bi-material is selected to prepare titanium system negative pole.
Table 1 embodiment 1-5 and the properties of product synopsis of comparative example 1-2
Claims (6)
1. a high power capacity titanium system negative material, it is characterised in that described negative material comprises lithium titanate and modified niobium
Two kinds of active materials of titanium oxide.
Negative material the most according to claim 1, it is characterised in that described modified niobium titanium oxide have with
Lower formula: TiNb2-xZrxO7-yC, wherein, 0 < x≤0.1,0 < y≤0.1.
Negative material the most according to claim 1, it is characterised in that described modified niobium titanium oxide accounts for two kinds
The 20%～80% of active material gross mass.
4. comprise a high power capacity titanium system negative pole for negative material described in claim 1-3 any claim, its
Being characterised by, described negative pole comprises described negative material, conductive agent and binding agent, wherein, described conduction
Agent comprises one or more in conductive black, acetylene black, carbon nano-fiber or CNT, described viscous
Knot agent is polyvinylidene fluoride.
5. a high power capacity titanium system negative electrode lithium ion electrokinetic cell, including positive pole, negative pole and electrolyte, its feature exists
In, described negative pole comprises the negative material described in claims 1 to 3 any claim, described positive pole
Comprise one or more active materials in cobalt acid lithium, LiMn2O4 or nickel-cobalt lithium manganate material.
6. a high power capacity titanium system negative electrode lithium ion electrokinetic cell, including positive pole, according to claim 4 negative
Pole and electrolyte, it is characterised in that described positive pole comprises cobalt acid lithium, LiMn2O4 or nickle cobalt lithium manganate material
One or more active materials in material.
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Cited By (9)
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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 |
| CN112510205A (en) * | 2019-09-13 | 2021-03-16 | 株式会社东芝 | Electrode, secondary battery, battery pack, and vehicle |
| GB2588254A (en) * | 2019-10-18 | 2021-04-21 | Echion Tech Limited | Li/Na-ion battery anode materials |
| GB2598432A (en) * | 2020-08-28 | 2022-03-02 | Echion Tech Limited | Active electrode material |
| CN114824155A (en) * | 2021-01-28 | 2022-07-29 | 丰田自动车株式会社 | All-solid-state battery |
| US11799077B2 (en) | 2020-06-03 | 2023-10-24 | Echion Technologies Limited | Active electrode material |
| US11831005B2 (en) | 2018-03-30 | 2023-11-28 | Kabushiki Kaisha Toshiba | Electrode group, battery, and battery pack |
| US11973220B2 (en) | 2020-08-28 | 2024-04-30 | Echion Technologies Limited | Active electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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| CN114824155A (en) * | 2021-01-28 | 2022-07-29 | 丰田自动车株式会社 | All-solid-state battery |
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