CN110247106A - A kind of mixing solid-liquid electrolytic cell with titanium niobate - Google Patents
A kind of mixing solid-liquid electrolytic cell with titanium niobate Download PDFInfo
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- CN110247106A CN110247106A CN201910442679.2A CN201910442679A CN110247106A CN 110247106 A CN110247106 A CN 110247106A CN 201910442679 A CN201910442679 A CN 201910442679A CN 110247106 A CN110247106 A CN 110247106A
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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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- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic electrolyte
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
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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 discloses a kind of mixing solid-liquid electrolytic cell with titanium niobate, is related to solid state battery field, includes mainly cathode, electrolyte and anode, the cathode includes TiNb2O7Negative electrode material, the TiNb2O7Negative electrode material is with TiNb2O7For core, and surface is coated with the shell of TiN or lithium titanate.By using above-mentioned technical proposal, TiN or lithium titanate are coated on titanium niobate surface, electrolyte can be completely cut off in this way and contacted with the direct of titanium niobate, so as to reduce the probability that titanium niobate surface forms SEI film, ensure that the capacitance that battery discharges for the first time.Also, anode uses the nickelic ternary material of high capacity and rich lithium material, by the high potential of titanium niobate, the practical charging voltage of reduction mixing solid-liquid battery, raising cyclical stability and by benefit lithium technology appropriate, so that TiNb2O7The N/P value of material cell tends to 1, and then improves positive and negative pole material utilization rate.
Description
Technical field
The present invention relates to solid state battery field, in particular to a kind of mixing solid-liquid electrolytic cell with titanium niobate.
Background technique
Lithium ion battery is widely applied in modern portable electronic devices, with high-energy density, high voltage, it is low from
Electric discharge, the advantages of operating temperature range is wide, long circulation life are also widely used for mixed power electric car (HEV) and greatly
Scale energy storage system (ESS).In order to meet growing energy demand, there are still many challenges, one of them is important
Challenge be improve battery safety and chemical property.TiNb2O7(TNO), theoretical specific capacity 387.6mAh/g, and
And there is excellent chemical property, it is considered one of most potential lithium ion battery negative material in recent years.It has height
Lithium ion be embedded in current potential (about 1.6V), think that TNO material will not generate SEI film always in pervious document report.
And the formation of SEI film can generate vital influence to the performance of electrode material.On the one hand, the formation of SEI film
Consume part lithium ion so that first charge-discharge irreversible capacity increases, and reduces the efficiency for charge-discharge of electrode material；It is another
Aspect, SEI film have organic solvent insoluble, can be stabilized in organic electrolyte solution, and solvent molecule cannot lead to
This layer of passivating film is crossed, to can effectively prevent the total insertion of solvent molecule, is avoided because solvent molecule is embedded in altogether to electrode material
Caused by destroy, thus substantially increase the cycle performance and service life of electrode.
Therefore, this be also TiNb2O7It is considered another key factor of suitable lithium ion battery negative material.
This conclusion is based on a widely accepted viewpoint: electrolyte solution can only be reduced in the case where being lower than 1.0V, however in reality
We have found that TNO material surface has the generation of SEI film in testing.As shown in Fig. 1, it is recycled 200 times for TNO electrode 0.1C
The SEM of test schemes, and TNO pole piece, which can be seen, has a thin layer of SEI film to generate, TNO material surface as indicated with an arrow.
Thus, directly select titanium niobate and common positive electrode to be assembled into lithium battery, that certainly will performance meeting to battery
It affects.Moreover, general positive electrode needs excess when battery design, i.e. N/P value is less than 1, so if reducing
Positive material utilization ratio is unfavorable for battery energy density performance.
Summary of the invention
The object of the present invention is to provide a kind of mixing solid-liquid electrolytic cell with titanium niobate, significantly reduce because
TiNb2O7It generates SEI film and is influenced caused by lithium battery performance.
Foregoing invention purpose of the invention has the technical scheme that a kind of mixing with titanium niobate
Solid-liquid electrolytic cell, including cathode, electrolyte and anode, the cathode include TiNb2O7Negative electrode material, the TiNb2O7
Negative electrode material is with TiNb2O7For core, and surface is coated with the shell of TiN or lithium titanate.
By using above-mentioned technical proposal, TiN or lithium titanate are coated on titanium niobate surface, lithium and niobium can be completely cut off in this way
The direct contact of sour titanium ensure that the capacitor that battery discharges for the first time so as to reduce the probability that titanium niobate surface forms SEI film
Amount.Secondly, TiN and lithium titanate have been also equipped with good electric conductivity, be conducive to the library for promoting the first charge-discharge of battery in this way
Human relations efficiency.
Preferably, the TiNb2O7It include metallic lithium powder in negative electrode material.
Preferably, the metallic lithium powder and TiNb2O7Mass ratio between negative electrode material is 0.1:(5~9).
Preferably, it is equipped with cushion gum layer between the anode and electrolyte, has electrolyte lithium salt in the cushion gum layer.
Preferably, the electrolyte lithium salt is one of LiBOB, LiODFB, LiFSI and LiTFSI.
Preferably, electrolyte is had in the electrolyte, and contains lithium salts in electrolyte.
Preferably, the lithium salts is one of trifluoroacetic acid lithium, lithium acetate, LiClO4, LiBF4 and LiAsF6 or several
Kind.
Preferably, with containing the positive electrode for mending lithium additive in the anode, the benefit lithium additive accounts for positive electrode
5~15wt% of weight.
Preferably, the benefit lithium additive is Li2NiO2、Li2IrO3、Li2MoO3、Li2RuO3、Li6MnO4、Li2Co0 .5Mn0 .5O2、Li2Ru0 .5Sn0 .5O2At least one of.
Above by the mode to addition lithium powder or lithium salts between anode, cathode, electrolyte and anode and electrolyte
Benefit lithium is carried out, consumed lithium during SEI film generates can be made up, effectively in this way so as to effectively guarantee lithium battery
Discharge capacity for the first time.
Preferably, the anode includes one of nickelic ternary material or rich lithium material.
By using above-mentioned technical proposal, energy density can be effectively improved in this way and avoids electrolyte under high voltage
It decomposes.
In conclusion advantageous effects of the invention are as follows:
1, using titanium niobate as core, and the shell of TiN or lithium titanate is coated on its surface, is guaranteeing titanium niobate electric conductivity in this way
Under the premise of energy, and it can reduce the probability that titanium niobate surface forms SEI film；
2, it by carrying out benefit lithium between anode, cathode, electrolyte or electrolyte and anode, can reduce due to activity in this way
Capacity attenuation caused by lithium loses；
3, using titanium niobate as negative electrode material, and using nickelic ternary material or rich lithium material as positive electrode, in this way can
It enough improves energy density while also can be avoided electrolyte under high voltage and decompose.
Detailed description of the invention
Fig. 1 is electron microscope of the conventional titanium niobate negative electrode material after discharging for the first time.
Specific embodiment
Embodiment one；
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate,
Step 1: by TiNb2O7Negative electrode material, conductive black and polyethylene glycol oxide are that 95:2:3 is incorporated in N- methyl with mass ratio
It is sufficiently mixed in pyrrolidones, negative electrode slurry is made；
Step 2: by negative electrode slurry even application on copper foil, and applied thickness is 25 μm, and in the case where temperature is 90 DEG C ~ 130 DEG C
It is dried, later again after roll-in and cutting, negative electrode tab is made；
Step 3: NCM811 material, conductive black and polyethylene glycol oxide-Kynoar are incorporated in mass ratio for 90:4:6
It is sufficiently mixed in tetrahydrofuran, anode sizing agent is made；
Step 4: by anode sizing agent even application on aluminium foil, and applied thickness is 25 μm, and is 110 DEG C ~ 150 DEG C in temperature
Under be dried, later again after roll-in and cutting, be made positive plate；
Step 5: lithium lanthanum zirconium oxygen, Kynoar and double trifluoromethayl sulfonic acid imines are melted with mass ratio for 90:5:5
It is uniformly mixed, is then coated on the two sides of PP film, and the applied thickness of two sides is 2.5mm；After solidification to be cooled is cut, obtain
Solid electrolyte；
Step 6: being 1 design according to N/P value, is covered with positive plate and negative electrode tab respectively in solid electrolyte two sides, and pass through roll-in
It after injection electrolyte, is fitted into battery packages, mixing solid-liquid battery is made.
Wherein, electrolyte is LiPF containing 1mol/L6EC-DEC-DMC mixed solution, the wherein volume of EC, DEC and DMC
Than for 1:1:1.
And TiNb2O7Negative electrode material is in TiNb2O7For core, using TiN as the core-shell structure of shell.And its preparation side
Method are as follows: S1, nanometer titanium niobate particle is uniformly mixed with nanometer lithium hydride particle by quality 1:0.05, obtains mixed raw material；S2,
Mixed raw material is placed under nitrogen atmosphere and is surface-treated 5h in 600 DEG C of progress high temperature, obtains nano modification titanium niobate particle；S3,
Nano modification titanium niobate particle is sintered 8h under 1000 DEG C of high temperature after hydrostatic profile, has obtained the TiNb of TiN cladding2O7Cathode
Material.
Embodiment two:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, is only that, just in the difference of embodiment one
Pole slurry is incorporated in tetrahydrofuran with mass ratio for 90:4:6 by NCA, conductive black and polyethylene glycol oxide-Kynoar to be filled
Divide and is mixed to get.
Embodiment three:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, is only that, just in the difference of embodiment one
Pole slurry is by Li1.1MnO2.1, conductive black and polyethylene glycol oxide-Kynoar with mass ratio be that 90:4:6 is incorporated in tetrahydro furan
It is sufficiently mixed to obtain in muttering.And TiNb2O7Negative electrode material is in TiNb2O7For core, using lithium titanate as the nucleocapsid knot of shell
Structure.Preparation method are as follows:
1., liquid processed: lithium titanate is added into ethyl alcohol, is stirred evenly, obtain lithium concentration be 15mol/L lithium titanate-second
Alcoholic solution；
2., cladding: by step 1. in lithium titanate-ethanol solution obtained pour into atomising device, carried out in the environment of nitrogen
Atomization, while titanium niobate powder being sprayed in lithium titanate-ethanol solution of atomization, cladding material is obtained after mixing well.Wherein,
The weight ratio of titanium niobate and lithium titanate is 1:0.2, and the partial size ratio of titanium niobate and lithium titanate is 1:0.05；
3., it is dry: by step 2. in cladding material obtained be placed in drying box, 80 DEG C at a temperature of dry 6h, it is complete to ethyl alcohol
After full volatilization, the TiNb of lithium titanate cladding is obtained2O7Negative electrode material.
Example IV:
It is a kind of mix solid-liquid battery preparation method, be only that in the difference of embodiment three, anode sizing agent by
Li1.17Ni0.25Mn0.58O2, conductive black and polyethylene glycol oxide-Kynoar with mass ratio be that 90:4:6 is incorporated in tetrahydro furan
It is sufficiently mixed to obtain in muttering.
Embodiment five:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, based on the basis of embodiment one, anode is starched
Also containing added with Li in material2NiO2, and Li2NiO2Account for the 5wt% of positive electrode after solidifying.
Embodiment six:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, based on the basis of embodiment two, anode is starched
Also containing added with Li in material2IrO3, and Li2IrO3Account for the 8wt% of positive electrode after solidifying.
Embodiment seven:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, based on the basis of embodiment three, anode is starched
Also containing added with Li in material2MoO3, and Li2MoO3Account for the 11wt% of positive electrode after solidifying.
Embodiment eight:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, based on the basis of example IV, anode is starched
Also containing added with Li in material2RuO3, and Li2RuO3Account for the 15wt% of positive electrode after solidifying.
In addition, it is Li that anode, which mends the benefit lithium additive that lithium can also add,6MnO4、Li2Co0 .5Mn0 .5O2、Li2Ru0 .5Sn0 .5O2、Li2S。
Embodiment nine:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, is based on the basis of embodiment one, cathode material
Also contain in material and be added with metallic lithium powder, and metallic lithium powder and TiNb2O7The mass ratio of negative electrode material is 0.1:5.
Embodiment ten:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, is based on the basis of embodiment two, cathode material
Also contain in material and be added with metallic lithium powder, and metallic lithium powder and TiNb2O7The mass ratio of negative electrode material is 0.1:7.
Embodiment 11:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, is based on the basis of embodiment one, cathode material
Also contain in material and be added with metallic lithium powder, and metallic lithium powder and TiNb2O7The mass ratio of negative electrode material is 0.1:9.
Embodiment 12:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, is based on the basis of embodiment one, electrolyte
In the also trifluoroacetic acid lithium containing 1mol/L.
Embodiment 13:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, is based on the basis of embodiment two, electrolyte
In also containing the LiClO of 1mol/L4。
Embodiment 14:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, is based on the basis of embodiment three, electrolyte
In also containing the LiBF of 1mol/L4。
Embodiment 15:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, is based on the basis of example IV, electrolyte
In also containing the LiAsF of 1mol/L6。
Also, lithium acetate can be contained in electrolyte.
Embodiment 16:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, based on the basis of embodiment one, anode and
Cushion gum layer, specific steps are as follows: (1) weigh 5 g cushion gum layer lithium salts LiTFSI and 1 g cushion gum layer are equipped between electrolyte
The two is dissolved in 114 g acetonitriles by additive PEO, forms the organic polyelectrolyte glue that solid content is 5%；(2) it is added slow
Rush glue-line inorganic solid electrolyte LLTO, mixing is dispersed into corresponding buffering adhesive, wherein cushion gum layer inorganic solid electrolyte
Weight accounts for the 40% of the weight of corresponding electrolyte buffer glue respectively.
Embodiment 17:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, based on the basis of embodiment two, anode and
Cushion gum layer, specific steps are as follows: (1) weigh 5 g cushion gum layer Lithium Salt LiBOBs and 1 g cushion gum layer adds are equipped between electrolyte
Add agent PEO, the two is dissolved in 114 g acetonitriles, forms the organic polyelectrolyte glue that solid content is 5%；(2) buffering is added
Glue-line inorganic solid electrolyte LLTO, mixing are dispersed into corresponding buffering adhesive, wherein the weight of cushion gum layer inorganic solid electrolyte
Amount accounts for the 40% of the weight of corresponding electrolyte buffer glue respectively.
Embodiment 18:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, based on the basis of embodiment three, anode and
Cushion gum layer, specific steps are as follows: (1) weigh 5 g cushion gum layer lithium salts LiODFB and 1 g cushion gum layer adds are equipped between electrolyte
Add agent PEO, the two is dissolved in 114 g acetonitriles, forms the organic polyelectrolyte glue that solid content is 5%；(2) buffering is added
Glue-line inorganic solid electrolyte LLTO, mixing are dispersed into corresponding buffering adhesive, wherein the weight of cushion gum layer inorganic solid electrolyte
Amount accounts for the 40% of the weight of corresponding electrolyte buffer glue respectively.
Embodiment 19:
A kind of preparation method of the mixing solid-liquid electrolytic cell with titanium niobate, based on the basis of example IV, anode and
Cushion gum layer, specific steps are as follows: (1) weigh 5 g cushion gum layer lithium salts LiFSI and 1 g cushion gum layer adds are equipped between electrolyte
Add agent PEO, the two is dissolved in 114 g acetonitriles, forms the organic polyelectrolyte glue that solid content is 5%；(2) buffering is added
Glue-line inorganic solid electrolyte LLTO, mixing are dispersed into corresponding buffering adhesive, wherein the weight of cushion gum layer inorganic solid electrolyte
Amount accounts for the 40% of the weight of corresponding electrolyte buffer glue respectively.
Comparative example one:
A kind of preparation method mixing solid-liquid battery, the difference with embodiment one is only that, TiNb2O7Negative electrode material is without nucleocapsid knot
Structure.
Comparative example two:
A kind of preparation method mixing solid-liquid battery, the difference with example IV are that cathode uses graphite material；
Above-described embodiment one to embodiment 19 and comparative example one and comparative example two are tested by following test method,
Obtain the test result such as table one and table two:
One embodiment one of table to embodiment ten each test result
| Test item | Implement Example one | Implement Example two | Implement Example three | Implement Example four | Implement Example five | Implement Example six | Implement Example seven | Implement Example eight | Implement Example nine | Embodiment Ten |
| First discharge specific capacity/mAh/g(with Titanium niobate quality meter) | 280 | 275 | 290 | 301 | 293 | 300 | 315 | 325 | 317 | 329 |
| Coulombic efficiency % for the first time | 90 | 91 | 91 | 92 | 93 | 92 | 91 | 92 | 99 | 98 |
| Capacity retention ratio % after 500 circles | 88 | 89 | 87 | 89 | 91 | 92 | 92 | 91 | 92 | 93 |
| Charge cutoff voltage V | 3.0 | 3.0 | 3.4 | 3.4 | 3.0 | 3.0 | 3.4 | 3.4 | 3.0 | 3.0 |
| Whether bulge | It is no | It is no | It is no | It is no | It is no | It is no | It is no | It is no | It is no | It is no |
Two embodiment 11 of table is to embodiment 19 and the test result of comparative example one and comparative example two
| Test item | Embodiment 11 | Implement Example ten Two | Implement Example ten Three | Implement Example ten Four | Implement Example ten Five | Implement Example ten Six | Implement Example ten Seven | Embodiment 18 | Embodiment 19 | Comparison Example one | Comparison Example two |
| First discharge specific capacity/mAh/ G(is in terms of titanium niobate quality) | 330 | 292 | 305 | 317 | 322 | 299 | 310 | 325 | 340 | 230 | / |
| Coulombic efficiency % for the first time | 99 | 95 | 96 | 94 | 96 | 97 | 96 | 95 | 97 | 83 | 80 |
| Capacity after 500 circles is kept Rate % | 93 | 92 | 91 | 93 | 93 | 93 | 94 | 94 | 93 | 83 | 53 |
| Charge cutoff voltage V | 3.0 | 3.0 | 3.0 | 3.4 | 3.4 | 3.0 | 3.0 | 3.4 | 3.4 | 3.0 | 5.0 |
| Whether bulge | It is no | It is no | It is no | It is no | It is no | It is no | It is no | It is no | It is no | It is no | Obviously Bulge |
Shown in table one and table two as above: coating TiN or lithium titanate on titanium niobate surface, electrolyte and niobic acid can be completely cut off in this way
The direct contact of titanium, so as to reduce the probability that titanium niobate surface forms SEI film, compared to comparative example 1, embodiment is for the first time
Specific discharge capacity significantly improves.Especially embodiment 5~19 by mend lithium technology, can further improve first discharge specific capacity with
And first charge-discharge coulombic efficiency.
Secondly, when selecting the nickelic ternary material of high capacity or rich lithium material as positive electrode, by the height of titanium niobate
Current potential can reduce the practical charging voltage (3.0~3.4V) of mixing solid-liquid battery, can reduce electrolyte so under high pressure
Decompose probability.Moreover, the battery from comparative example two with graphite cathode (5.0V), it can be seen that have obvious bulge, this illustrates electricity
Electrolyte inside pond has been likely to occur decomposition.
Thus, lower voltage charges, and is also beneficial to improve the cyclical stability of battery, and pass through benefit lithium skill appropriate
Art, additionally it is possible to the N/P value of positive and negative anodes be maintained 1, improve the utilization rate of positive and negative pole material.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
Claims (10)
1. a kind of mixing solid-liquid electrolytic cell with titanium niobate, including cathode, electrolyte and anode, it is characterised in that: institute
Stating cathode includes TiNb2O7Negative electrode material, the TiNb2O7Negative electrode material is with TiNb2O7For core, and surface is coated with
The shell of TiN or lithium titanate.
2. a kind of mixing solid-liquid electrolytic cell with titanium niobate according to claim 1, it is characterised in that: described
TiNb2O7It include metallic lithium powder in negative electrode material.
3. a kind of mixing solid-liquid electrolytic cell with titanium niobate according to claim 3, it is characterised in that: the gold
Belong to lithium powder and TiNb2O7Mass ratio between negative electrode material is 0.1:(5~9).
4. a kind of mixing solid-liquid electrolytic cell with titanium niobate according to claim 1, it is characterised in that: it is described just
It is equipped with cushion gum layer between pole and electrolyte, has electrolyte lithium salt in the cushion gum layer.
5. a kind of mixing solid-liquid electrolytic cell with titanium niobate according to claim 4, it is characterised in that: the electricity
Solving matter lithium salts is one of LiBOB, LiODFB, LiFSI and LiTFSI.
6. a kind of mixing solid-liquid electrolytic cell with titanium niobate according to claim 1, it is characterised in that: the electricity
Xie Zhizhong has electrolyte, and contains lithium salts in electrolyte.
7. a kind of mixing solid-liquid electrolytic cell with titanium niobate according to claim 1, it is characterised in that: the lithium
Salt is one or more of trifluoroacetic acid lithium, lithium acetate, LiClO4, LiBF4 and LiAsF6.
8. a kind of mixing solid-liquid electrolytic cell with titanium niobate according to claim 1, it is characterised in that: it is described just
With containing the positive electrode for mending lithium additive in extremely, the benefit lithium additive accounts for 5~15wt% of positive electrode weight.
9. a kind of mixing solid-liquid electrolytic cell with titanium niobate according to claim 1, it is characterised in that: the benefit
Lithium additive is Li2NiO2、Li2IrO3、Li2MoO3、Li2RuO3、Li6MnO4、Li2Co0 .5Mn0 .5O2、Li2Ru0 .5Sn0 .5O2
At least one of.
10. a kind of mixing solid-liquid electrolytic cell with titanium niobate according to claim 1, it is characterised in that: described
Anode includes one of nickelic ternary material or rich lithium material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110943207A (en) * | 2019-10-28 | 2020-03-31 | 浙江锋锂新能源科技有限公司 | Modified TiNb2O7Material and modification method |
| CN112271290A (en) * | 2020-10-14 | 2021-01-26 | 华中科技大学 | Method for preparing lithium-containing titanium niobate (LTNO) material or negative electrode and application |
| CN112490490A (en) * | 2020-11-09 | 2021-03-12 | 深圳市比克动力电池有限公司 | Lithium ion battery |
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