CN110247106B - Mixed solid-liquid electrolyte battery with titanium niobate - Google Patents
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Abstract
The invention discloses a mixed solid-liquid electrolyte battery with titanium niobate, which relates to the field of solid batteries and mainly comprises a negative electrode, an electrolyte and a positive electrode, wherein the negative electrode contains TiNb2O7Negative electrode material of said TiNb2O7The cathode material is TiNb2O7Is a core, and the surface of the core is coated with a TiN or lithium titanate shell layer. By adopting the technical scheme, the surface of the titanium niobate is coated with TiN or lithium titanate, so that the direct contact between the electrolyte and the titanium niobate can be isolated, the probability of forming an SEI film on the surface of the titanium niobate can be reduced, and the first discharge capacity of the battery is ensured. In addition, the anode adopts a high-capacity high-nickel ternary material and a lithium-rich material, the actual charging voltage of the hybrid solid-liquid battery is reduced by means of the high potential of the titanium niobate, the cycling stability is improved, and TiNb is enabled to be obtained through a proper lithium supplement technology2O7The N/P value of the material battery tends to 1, and the utilization rate of the anode and cathode materials is further improved.
Description
Technical Field
The invention relates to the field of solid batteries, in particular to a mixed solid-liquid electrolyte battery with titanium niobate.
Background
Lithium ion batteries are widely used in modern portable electronic devices, have the advantages of high energy density, high voltage, low self-discharge, wide operating temperature range, and long cycle life, and are also widely used in Hybrid Electric Vehicles (HEVs) and large-scale Energy Storage Systems (ESS). To meet the increasing energy demand, many challenges still remain, one of which is to improve the safety and electrochemical performance of the battery. TiNb2O7(TNO), which has a theoretical specific capacity of 387.6mAh/g and excellent electrochemical properties, has recently been considered as one of the most potential negative electrode materials for lithium ion batteries. It has a high lithium ion intercalation potential (about 1.6V), and it has been considered in previous literature reports that TNO materials do not generate SEI films.
The formation of the SEI film has a crucial influence on the performance of the electrode material. On one hand, the formation of the SEI film consumes part of lithium ions, so that the irreversible capacity of the first charge and discharge is increased, and the charge and discharge efficiency of the electrode material is reduced; on the other hand, the SEI film has organic solvent insolubility and can stably exist in an organic electrolyte solution, and solvent molecules cannot pass through the passivation film, so that co-embedding of the solvent molecules can be effectively prevented, damage to an electrode material due to the co-embedding of the solvent molecules is avoided, and the cycle performance and the service life of the electrode are greatly improved.
Therefore, this is also TiNb2O7Is deemed to be appropriateAnother important factor of the lithium ion battery negative electrode material. This conclusion is based on a widely accepted view: the electrolyte solution can only be reduced at less than 1.0V, however, in the experiment, the SEI film is generated on the surface of the TNO material. As shown in fig. 1, which is an SEM image of the TNO electrode tested 200 times in 0.1C cycle, the TNO pole piece surface can be seen to have a thin SEI film formed, as indicated by the arrows on the surface of the TNO material.
Therefore, the lithium battery is directly assembled by selecting the titanium niobate and the common anode material, and certain influence is certainly caused on the performance of the battery. In addition, in battery design, the positive electrode material generally needs to be excessive, that is, the N/P value is less than 1, and therefore, if the utilization rate of the positive electrode material is reduced, it is not favorable for the energy density of the battery to be exerted.
Disclosure of Invention
It is an object of the present invention to provide a mixed solid-liquid electrolyte battery with titanium niobate which effectively reduces TiNb2O7The influence of the SEI film on the performance of the lithium battery.
The above object of the present invention is achieved by the following technical solutions: a mixed solid-liquid electrolyte battery with titanium niobate comprises a negative electrode, an electrolyte and a positive electrode, wherein the negative electrode contains TiNb2O7Negative electrode material of said TiNb2O7The cathode material is TiNb2O7Is a core, and the surface of the core is coated with a TiN or lithium titanate shell layer.
By adopting the technical scheme, the surface of the titanium niobate is coated with TiN or lithium titanate, so that the direct contact between lithium and the titanium niobate can be isolated, the probability of forming an SEI film on the surface of the titanium niobate can be reduced, and the first discharge capacity of the battery is ensured. Secondly, the TiN and the lithium titanate also have good conductive performance, so that the coulomb efficiency of the first charge and discharge of the battery is improved.
Preferably, the TiNb is2O7The negative electrode material contains metallic lithium powder.
Preferably, the lithium metal powder and TiNb2O7The mass ratio of the negative electrode materials is 0.1 (5-9).
Preferably, a buffer glue layer is arranged between the positive electrode and the electrolyte, and electrolyte lithium salt is carried in the buffer glue layer.
Preferably, the electrolyte lithium salt is one of LiBOB, LiODFB, LiFSI, and LiTFSI.
Preferably, the electrolyte is provided with an electrolytic solution, and the electrolytic solution contains a lithium salt.
Preferably, the lithium salt is one or more of lithium trifluoroacetate, lithium acetate, LiClO4, LiBF4 and LiAsF 6.
Preferably, the positive electrode is provided with a positive electrode material containing a lithium supplement additive, and the lithium supplement additive accounts for 5-15 wt% of the weight of the positive electrode material.
Preferably, the lithium supplement additive is Li2NiO2、Li2IrO3、Li2MoO3、Li2RuO3、Li6MnO4、Li2Co0 .5Mn0 .5O2、Li2Ru0 .5Sn0 .5O2At least one of (1).
The lithium is supplemented in a mode of adding the lithium powder or the lithium salt to the anode, the cathode, the electrolyte and between the anode and the electrolyte, so that the lithium consumed in the SEI film generation process can be effectively compensated, and the first discharge capacity of the lithium battery can be effectively ensured.
Preferably, the positive electrode comprises one of a high nickel ternary material or a lithium-rich material.
By adopting the technical scheme, the energy density can be effectively improved, and the decomposition of the electrolyte under high voltage can be avoided.
In conclusion, the beneficial technical effects of the invention are as follows:
1. the titanium niobate is taken as a core, and the surface of the titanium niobate is coated with a TiN or lithium titanate shell layer, so that the probability of forming an SEI film on the surface of the titanium niobate can be reduced on the premise of ensuring the conductivity of the titanium niobate;
2. by supplementing lithium between the positive electrode, the negative electrode, the electrolyte or the electrolyte and the positive electrode, capacity fade due to active lithium loss can be reduced;
3. titanium niobate is used as a negative electrode material, and a high-nickel ternary material or a lithium-rich material is used as a positive electrode material, so that the energy density can be improved, and the decomposition of the electrolyte under high voltage can be avoided.
Drawings
Fig. 1 is an electron microscope image of a conventional titanium niobate negative electrode material after first discharge.
Detailed Description
The first embodiment;
a method for preparing a mixed solid-liquid electrolyte battery with titanium niobate,
step one, TiNb2O7The negative electrode material, the conductive carbon black and the polyethylene oxide are mixed according to the mass ratio of 95: 2: 3, adding the mixture into N-methyl pyrrolidone for full mixing to prepare cathode slurry;
step two, uniformly coating the negative electrode slurry on copper foil, wherein the coating thickness is 25 micrometers, drying at the temperature of 90-130 ℃, and then rolling and cutting to obtain a negative electrode sheet;
step three, mixing the NCM811 material, the conductive carbon black and the polyoxyethylene-polyvinylidene fluoride according to the mass ratio of 90: 4: 6, adding the mixture into tetrahydrofuran, and fully mixing to prepare anode slurry;
step four: uniformly coating the positive electrode slurry on an aluminum foil, wherein the coating thickness is 25 mu m, drying at the temperature of 110-150 ℃, and then rolling and cutting to obtain a positive electrode sheet;
step five: lithium lanthanum zirconium oxide, polyvinylidene fluoride and bis (trifluoromethane) sulfonic acid imine are mixed according to the mass ratio of 90: 5: 5, uniformly melting and mixing, and then coating the mixture on two sides of the PP film, wherein the coating thickness of the two sides is 2.5 mm; after cooling, solidifying and cutting, obtaining a solid electrolyte;
step six: and respectively coating a positive plate and a negative plate on two sides of the solid electrolyte according to the design that the N/P value is 1, rolling and injecting electrolyte, and then filling the electrolyte into a battery package to obtain the mixed solid-liquid battery.
Wherein the electrolyte contains 1mol/L LiPF6The EC-DEC-DMC mixed solution of (1), wherein the volume ratio of EC, DEC and DMC is 1: 1: 1.
and TiNb2O7The cathode material is TiNb2O7A core-shell structure taking TiN as a shell layer. The preparation method comprises the following steps: s1, mixing the nanometer titanium niobate particles and the nanometer lithium hydride particles according to the mass ratio of 1:0.05, uniformly mixing to obtain a mixed raw material; s2, placing the mixed raw materials in a nitrogen atmosphere, and performing high-temperature surface treatment for 5 hours at 600 ℃ to obtain nano modified titanium niobate particles; s3, sintering the nano modified titanium niobate particles at 1000 ℃ for 8h after static pressure forming to obtain TiNb coated with TiN2O7And (3) a negative electrode material.
Example two:
the preparation method of the mixed solid-liquid electrolyte battery with the titanium niobate only differs from the first embodiment in that the positive electrode slurry is prepared by mixing NCA, conductive carbon black and polyoxyethylene-polyvinylidene fluoride in a mass ratio of 90: 4: 6 adding into tetrahydrofuran and mixing.
Example three:
the preparation method of the mixed solid-liquid electrolyte battery with the titanium niobate only differs from the first embodiment in that the anode slurry is made of Li1.1MnO2.1The conductive carbon black and the polyoxyethylene-polyvinylidene fluoride are mixed according to the mass ratio of 90: 4: 6 adding into tetrahydrofuran and mixing. And TiNb2O7The cathode material is TiNb2O7The core-shell structure takes lithium titanate as a shell layer. The preparation method comprises the following steps:
firstly, preparing liquid: adding lithium titanate into ethanol, and uniformly stirring to obtain a lithium titanate-ethanol solution with the lithium ion concentration of 15 mol/L;
secondly, coating: filling the lithium titanate-ethanol solution prepared in the step I into an atomization device, atomizing in a nitrogen environment, spraying the titanium niobate powder into the atomized lithium titanate-ethanol solution, and fully and uniformly mixing to obtain the coating material. Wherein the weight ratio of the titanium niobate to the lithium titanate is 1:0.2, and the particle diameter ratio of the titanium niobate to the lithium titanate is 1: 0.05;
③ toDrying: placing the coating material prepared in the step II in a drying oven, drying at the temperature of 80 ℃ for 6 hours, and obtaining lithium titanate coated TiNb after the ethanol is completely volatilized2O7And (3) a negative electrode material.
Example four:
a method for preparing a mixed solid-liquid battery, which is different from the third embodiment only in that the positive electrode slurry is made of Li1.17Ni0.25Mn0.58O2The conductive carbon black and the polyoxyethylene-polyvinylidene fluoride are mixed according to the mass ratio of 90: 4: 6 adding into tetrahydrofuran and mixing.
Example five:
based on the first embodiment, the positive electrode slurry also contains Li2NiO2And Li2NiO2Accounting for 5wt% of the cured cathode material.
Example six:
based on the second embodiment, the preparation method of the mixed solid-liquid electrolyte battery with the titanium niobate further comprises the step of adding Li into the positive electrode slurry2IrO3And Li2IrO3Accounting for 8wt percent of the solidified anode material.
Example seven:
based on the third embodiment, the positive electrode slurry also contains Li2MoO3And Li2MoO3Accounting for 11wt% of the cured cathode material.
Example eight:
based on the fourth embodiment, the positive electrode slurry also contains Li2RuO3And Li2RuO3Accounting for 15wt% of the cured cathode material.
In addition, Li can be added as a lithium supplement additive for lithium supplement of the positive electrode6MnO4、Li2Co0 .5Mn0 .5O2、Li2Ru0 .5Sn0 .5O2、Li2S。
Example nine:
based on the first embodiment, the negative electrode material also contains metal lithium powder, and the metal lithium powder and TiNb are added2O7The mass ratio of the anode material is 0.1: 5.
example ten:
based on the second embodiment, the negative electrode material also contains metal lithium powder, and the metal lithium powder and TiNb are added2O7The mass ratio of the negative electrode material is 0.1: 7.
example eleven:
based on the first embodiment, the negative electrode material also contains metal lithium powder, and the metal lithium powder and TiNb are added2O7The mass ratio of the anode material is 0.1: 9.
example twelve:
based on the first embodiment, the electrolyte also contains 1mol/L lithium trifluoroacetate.
Example thirteen:
based on the second embodiment, the electrolyte also contains 1mol/L LiClO4。
Example fourteen:
based on the third embodiment, the electrolyte also contains 1mol/L LiBF4。
Example fifteen:
based on the fourth embodiment, the electrolyte also contains 1mol/L LiAsF6。
The electrolyte may contain lithium acetate.
Example sixteen:
a preparation method of a mixed solid-liquid electrolyte battery with titanium niobate is based on the first embodiment, wherein a buffer glue layer is arranged between a positive electrode and an electrolyte, and the preparation method comprises the following specific steps: (1) weighing 5 g of lithium salt LiTFSI of the buffer adhesive layer and 1 g of PEO (polyethylene oxide) of the buffer adhesive layer, and dissolving the lithium salt LiTFSI and the PEO in 114 g of acetonitrile to form an organic polymer electrolyte adhesive with solid content of 5%; (2) adding buffer glue layer inorganic solid electrolyte LLTO, mixing and dispersing to obtain corresponding buffer glue, wherein the weight of the buffer glue layer inorganic solid electrolyte accounts for 40% of the weight of the corresponding electrolyte buffer glue.
Example seventeen:
a preparation method of a mixed solid-liquid electrolyte battery with titanium niobate is based on the second embodiment, and a buffer glue layer is arranged between a positive electrode and an electrolyte, and the preparation method specifically comprises the following steps: (1) weighing 5 g of lithium salt LiBOB of the buffer adhesive layer and 1 g of PEO of the buffer adhesive layer, and dissolving the lithium salt LiBOB and the PEO in 114 g of acetonitrile to form organic polymer electrolyte adhesive with solid content of 5%; (2) adding buffer glue layer inorganic solid electrolyte LLTO, mixing and dispersing to obtain corresponding buffer glue, wherein the weight of the buffer glue layer inorganic solid electrolyte accounts for 40% of the weight of the corresponding electrolyte buffer glue.
Example eighteen:
a preparation method of a mixed solid-liquid electrolyte battery with titanium niobate is based on the third embodiment, and a buffer glue layer is arranged between a positive electrode and an electrolyte, and the preparation method specifically comprises the following steps: (1) weighing 5 g of lithium salt LiODFB and 1 g of PEO as a buffer layer additive, and dissolving the LiODFB and the PEO in 114 g of acetonitrile to form an organic polymer electrolyte adhesive with solid content of 5%; (2) adding buffer glue layer inorganic solid electrolyte LLTO, mixing and dispersing to obtain corresponding buffer glue, wherein the weight of the buffer glue layer inorganic solid electrolyte accounts for 40% of the weight of the corresponding electrolyte buffer glue.
Example nineteenth:
a preparation method of a mixed solid-liquid electrolyte battery with titanium niobate is based on the fourth embodiment, and a buffer glue layer is arranged between a positive electrode and an electrolyte, and the preparation method specifically comprises the following steps: (1) weighing 5 g of lithium salt LiFSI of the buffer adhesive layer and 1 g of PEO of the buffer adhesive layer, and dissolving the lithium salt LiFSI and the PEO in 114 g of acetonitrile to form an organic polymer electrolyte adhesive with solid content of 5%; (2) adding buffer glue layer inorganic solid electrolyte LLTO, mixing and dispersing to obtain corresponding buffer glue, wherein the weight of the buffer glue layer inorganic solid electrolyte accounts for 40% of the weight of the corresponding electrolyte buffer glue.
Comparative example one:
the preparation method of the mixed solid-liquid battery is only different from the first embodiment in that TiNb2O7The cathode material has no core-shell structure.
Comparative example two:
the preparation method of the mixed solid-liquid battery is different from the fourth embodiment in that the negative electrode adopts a graphite material;
the above-described examples one to nineteen and comparative examples one and two were tested by the following test methods to obtain the test results as shown in tables one and two:
TABLE test results of examples one to ten
| Test items | Example one | Example two | EXAMPLE III | Example four | EXAMPLE five | EXAMPLE six | EXAMPLE seven | Example eight | Example nine | Example ten |
| Specific capacity of first discharge/mAh/g (in terms of titanium niobate quality) | 280 | 275 | 290 | 301 | 293 | 300 | 315 | 325 | 317 | 329 |
| First coulombic efficiency% | 90 | 91 | 91 | 92 | 93 | 92 | 91 | 92 | 99 | 98 |
| Capacity retention after 500 cycles% | 88 | 89 | 87 | 89 | 91 | 92 | 92 | 91 | 92 | 93 |
| Cut-off voltage V for charging | 3.0 | 3.0 | 3.4 | 3.4 | 3.0 | 3.0 | 3.4 | 3.4 | 3.0 | 3.0 |
| Whether bulge or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not |
Table two test results of eleven to nineteen examples and comparative examples one and two
| Test items | Example ten A | Example ten II | Example ten III | Example ten Fourthly | Example ten Five of them | Example ten Six ingredients | Example ten Seven-piece | Example ten Eight-part | Example ten Nine-piece | Comparative example A | Comparative example II |
| Specific capacity of first discharge/mAh/g (titanium niobate) Mass meter | 330 | 292 | 305 | 317 | 322 | 299 | 310 | 325 | 340 | 230 | / |
| First coulombic efficiency% | 99 | 95 | 96 | 94 | 96 | 97 | 96 | 95 | 97 | 83 | 80 |
| Capacity retention after 500 cycles% | 93 | 92 | 91 | 93 | 93 | 93 | 94 | 94 | 93 | 83 | 53 |
| Cut-off voltage V for charging | 3.0 | 3.0 | 3.0 | 3.4 | 3.4 | 3.0 | 3.0 | 3.4 | 3.4 | 3.0 | 5.0 |
| Whether bulge or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Obvious drum Bag (bag) |
As shown in tables one and two above: the TiN or lithium titanate is coated on the surface of the titanium niobate, so that the direct contact between the electrolyte and the titanium niobate can be isolated, the probability of forming an SEI film on the surface of the titanium niobate can be reduced, and compared with the comparative example 1, the specific capacity of the first discharge of the embodiment is obviously improved. Especially, in the embodiments 5 to 19, the first discharge specific capacity and the first charge-discharge coulombic efficiency can be further improved by the lithium supplement technology.
Secondly, when a high-capacity high-nickel ternary material or a lithium-rich material is selected as a positive electrode material, the actual charging voltage (3.0-3.4V) of the mixed solid-liquid battery can be reduced by virtue of the high potential of the titanium niobate, so that the decomposition probability of the electrolyte under high pressure can be reduced. Also, from the battery with the graphite negative electrode (5.0V) of comparative example two, it can be seen that there is a significant swelling, which indicates that decomposition of the electrolyte inside the battery may occur.
Therefore, the charging at a lower voltage is also beneficial to improving the cycling stability of the battery, and the N/P values of the positive electrode and the negative electrode can be maintained at 1 through a proper lithium supplement technology, so that the utilization rate of the positive electrode and the negative electrode materials is improved.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (9)
1. The utility model provides a mix solid-liquid electrolyte battery with titanium niobate, includes negative pole, electrolyte and positive pole, its characterized in that: the negative electrode contains TiNb2O7Negative electrode material of said TiNb2O7The cathode material is TiNb2O7Is a core, the surface of which is coated with TiN, the TiNb2O7The negative electrode material also contains metal lithium powder; the TiNb2O7The preparation method of the cathode material comprises the following steps: s1, mixing the nanometer titanium niobate particles and the nanometer lithium hydride particles according to the mass ratio of 1:0.05, uniformly mixing to obtain a mixed raw material; s2, placing the mixed raw materials in a nitrogen atmosphere, and performing high-temperature surface treatment for 5 hours at 600 ℃ to obtain nano modified titanium niobate particles; s3, sintering the nano modified titanium niobate particles at 1000 ℃ for 8h after static pressure forming to obtain TiNb coated with TiN2O7And (3) a negative electrode material.
2. The mixed solid-liquid electrolyte battery with titanium niobate of claim 1, wherein: the metal lithium powder and TiNb2O7The mass ratio of the negative electrode materials is 0.1 (5-9).
3. The mixed solid-liquid electrolyte battery with titanium niobate of claim 1, wherein: and a buffer glue layer is arranged between the anode and the electrolyte, and electrolyte lithium salt is carried in the buffer glue layer.
4. The mixed solid-liquid electrolyte battery with titanium niobate of claim 3, wherein: the electrolyte lithium salt is one of LiBOB, LiODFB, LiFSI and LiTFSI.
5. The mixed solid-liquid electrolyte battery with titanium niobate of claim 1, wherein: the electrolyte is provided with an electrolyte, and the electrolyte contains lithium salt.
6. The mixed solid-liquid electrolyte battery with titanium niobate according to claim 5, characterized in that: the lithium salt is one or more of lithium trifluoroacetate, lithium acetate, LiClO4, LiBF4 and LiAsF 6.
7. The mixed solid-liquid electrolyte battery with titanium niobate of claim 1, wherein: the positive electrode is provided with a positive electrode material containing a lithium supplement additive, and the lithium supplement additive accounts for 5-15 wt% of the weight of the positive electrode material.
8. The mixed solid-liquid electrolyte battery with titanium niobate of claim 7, wherein: the lithium supplement additive is Li2NiO2、Li2IrO3、Li2MoO3、Li2RuO3、Li6MnO4、Li2Co0 .5Mn0 .5O2、Li2Ru0 .5Sn0 .5O2At least one of (1).
9. The mixed solid-liquid electrolyte battery with titanium niobate of claim 1, wherein: the positive electrode comprises one of a high nickel ternary material or a lithium-rich material.
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| 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 |
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| JP6570934B2 (en) * | 2015-09-16 | 2019-09-04 | 株式会社東芝 | Battery active materials, electrodes, non-aqueous electrolyte batteries, battery packs and vehicles |
| CN108539150A (en) * | 2018-03-26 | 2018-09-14 | 合肥国轩高科动力能源有限公司 | A kind of comprehensive silicon negative material and preparation method thereof |
| CN109768318A (en) * | 2019-03-12 | 2019-05-17 | 浙江锋锂新能源科技有限公司 | A kind of mixing solid-liquid electrolyte lithium battery |
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