CN109167049A - A kind of graphene coated titanium niobium oxide combination electrode material, lithium primary battery and preparation method - Google Patents
A kind of graphene coated titanium niobium oxide combination electrode material, lithium primary battery and preparation method Download PDFInfo
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- CN109167049A CN109167049A CN201811131999.8A CN201811131999A CN109167049A CN 109167049 A CN109167049 A CN 109167049A CN 201811131999 A CN201811131999 A CN 201811131999A CN 109167049 A CN109167049 A CN 109167049A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 81
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 57
- 239000007772 electrode material Substances 0.000 title claims abstract description 47
- OBOYOXRQUWVUFU-UHFFFAOYSA-N [O-2].[Ti+4].[Nb+5] Chemical compound [O-2].[Ti+4].[Nb+5] OBOYOXRQUWVUFU-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000010936 titanium Substances 0.000 claims abstract description 27
- 239000010955 niobium Substances 0.000 claims abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 16
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 claims abstract description 5
- 239000007773 negative electrode material Substances 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 claims description 3
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 2
- 239000006256 anode slurry Substances 0.000 claims 1
- 239000006257 cathode slurry Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 5
- 239000000843 powder Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 238000000498 ball milling Methods 0.000 description 11
- 238000007599 discharging Methods 0.000 description 11
- 229910010379 TiNb2O7 Inorganic materials 0.000 description 9
- 229920006373 Solef Polymers 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- YSZJKUDBYALHQE-UHFFFAOYSA-N rhenium trioxide Chemical group O=[Re](=O)=O YSZJKUDBYALHQE-UHFFFAOYSA-N 0.000 description 4
- 239000012212 insulator Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910002785 ReO3 Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000008111 motor development Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- -1 titanium niobium oxide compound Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
It includes TiNb that the present invention, which provides a kind of graphene coated titanium niobium oxide combination electrode material, lithium primary battery and preparation method, combination electrode material,xO(2+2.5x)Kernel and graphene coated layer, the mass fraction of graphene coated layer are 0.01%-5%, wherein x 1.8-2.3.Preparation method includes being sintered to obtain TiNb after mixing titanium source and niobium sourcexO(2+2.5x)Material；By gained TiNbxO(2+2.5x)Sintering obtains graphene coated titanium niobium oxide combination electrode material after material is mixed with graphene or graphene presoma.Lithium primary battery is using above-mentioned graphene coated titanium niobium oxide combination electrode material as positive electrode active materials, using lithium as negative electrode active material.The combination electrode material utilizes TiNbxO(2+2.5x)High lithium storage content and the good conductive characteristic of graphene, using graphene coated TiNbxO(2+2.5x)Material greatly promotes the performance of material gram volume and high rate performance.Preparation method is simple, at low cost.The lithium primary battery energy density is high, and high safety and reliability has heavy current pulse characteristic.
Description
Technical field
The invention belongs to technical field of lithium ion battery electrode, aoxidize more particularly, to a kind of graphene coated titanium niobium
Object combination electrode material, lithium primary battery and preparation method.
Background technique
Lithium primary battery has the advantages such as energy density height, light weight, small in size, is widely used in various electronic equipments
Main power source and memory ready power supply with the optimization and upgrading of automobile, are expected to develop lithium primary battery in vehicle field in recent years
Purposes.Based on such background, it is desirable that in the state of being maintained as the high-energy density of feature of lithium primary battery, improve lithium
The security performance of one-shot battery improves output characteristics, particularly pulse (interval) the electric discharge spy as instantaneous large current characteristic
Property is most important.Traditional lithium primary battery does not have high current pulsed discharge characteristic, therefore is not able to satisfy Hyundai Motor development
It needs.
From 2010, professor Goodenough reported TiNb2O7After material has storage lithium performance, TiNb2O7Material causes
Industry concern.Titanium niobium oxide TiNbxO7 belongs to " shear surface ReO3 structure ", this structure is more suitable for lithium than simple ReO3
The insertion and abjection of ion, and its space structure does not change substantially, therefore it is safer in process of intercalation；And embedding de-
During lithium, the transfer of 5 electronics can occur, correspond to the redox reaction of 5 electricity pair, theoretical capacity is
387.6mAh/g.Therefore, safety is high as lithium titanate, but capacity can increase by four at as electrode of lithium cell material
Material has boundless prospect.But TiNb2O7Almost insulator, conductivity is low, uses as electrode material of lithium battery
When, the problem of being greatly reduced there are still capacity when output power.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of graphene coated titanium niobium oxide combination electrode material, lithium are once electric
Pond and preparation method, graphene has good conductivity, by graphene and TiNbxO(2+2.5x)It is compound that conductivity can be obtained is preferable
Class graphene coated TiNbxO(2+2.5x)Combination electrode material substantially improves the performance of electrode material charge and discharge, obtained lithium one
Primary cell energy density is high, and high safety and reliability has heavy current pulse characteristic.
In order to solve the above technical problems, it is an object of the present invention to provide a kind of graphene coated titanium niobium oxide is compound
Electrode material, including TiNbxO(2+2.5x)Kernel and graphene coated layer, the mass fraction of graphene coated layer are 0.01%-
5%, wherein x 1.8-2.3, it is preferred that the mass fraction of graphene coated layer is 0.1%-2%, it is preferred that x 1.9-
2.0。
Above-mentioned graphene coated titanium niobium oxide combination electrode material is prepared it is a further object of the present invention to provide a kind of
Method, it is characterised in that: include:
Sintering after titanium source and the mixing of niobium source is obtained TiNb by the first stepxO(2+2.5x)Material, it is preferred that titanium source is rubbed with niobium source
You are than being Ti:Nb=1:1.5-1:2.5；
Second step, by TiNb obtained by the first stepxO(2+2.5x)Material is sintered after mixing with graphene or graphene presoma
To graphene coated titanium niobium oxide combination electrode material.
In technical solution, it is preferred that titanium source is metatitanic acid, titanium dioxide, butyl titanate, isopropyl titanate and titanium oxyoxalate
One of or a variety of combinations, it is preferred that titanium dioxide be Detitanium-ore-type titanium dioxide or rutile titanium dioxide.
In technical solution, it is preferred that niobium source is one of niobium oxalate, niobic acid and niobium pentaoxide or a variety of combinations.
In technical solution, it is preferred that the sintering temperature in the first step is 800 DEG C -1500 DEG C, it is preferred that in the first step
Sintering temperature is 1000 DEG C -1400 DEG C.
In technical solution, it is preferred that the sintering temperature in second step is 400 DEG C -1000 DEG C, it is preferred that in second step
Sintering temperature is 500 DEG C -800 DEG C.
In technical solution, it is preferred that second step includes: by the resulting TiNb of the first stepxO(2+2.5x)Material and graphene or
The mixing of graphene presoma, and ground, is spraying, it is then sintered, obtains graphene coated titanium niobium oxide compound electric
Pole material.
In technical solution, it is preferred that in second step, the partial size D50 of the particle obtained after grinding is 0.001 μm -5 μm, excellent
Choosing, the partial size D50 of the particle obtained after grinding is 0.05 μm -1 μm.
In technical solution, it is preferred that in second step, the partial size D50 of the particle obtained after spraying is 4-50 μm, it is preferred that
The partial size D50 of the particle obtained after spraying is 8-20 μm.
Another object of the present invention is to provide a kind of lithium primary battery, and lithium primary battery is with above-mentioned graphene coated titanium niobium
Oxide combination electrode material is positive electrode active materials, using lithium as negative electrode active material.
In technical solution, it is preferred that lithium primary battery is button, cylindrical type, square or Soft Roll formula battery.
It is yet another object of the invention to provide the methods for preparing above-mentioned lithium primary battery, including successively carry out: preparing positive and negative
Pole slurry；Coating sizing-agent；It rolls；Punching；Baking；Fluid injection.
The advantages and positive effects of the present invention are: graphene coated TiNb of the inventionxO(2+2.5x)Combination electrode material
Material utilizes TiNbxO(2+2.5x)High lithium storage content and the good conductive characteristic of graphene, using graphene coated TiNbxO(2+2.5x)
Material greatly improves the performance of material gram volume and high rate performance.The preparation method of combination electrode material is simple, at low cost, material
Expect that consistency is good.The energy density of the lithium primary battery is high, and high safety and reliability has heavy current pulse characteristic.
Specific embodiment
TiNb2O7Have excellent storage lithium performance, safety is high as lithium titanate, but capacity can increase by four at,
There are boundless prospect, still, TiNb as electrode material of lithium battery2O7Almost insulator, conductivity is low, as lithium
Battery electrode material there are still capacity when output power in use, the problem of being greatly reduced, as described in following comparative example:
Titanium dioxide 23.42g and the 76.58g niobium pentaoxide of Detitanium-ore-type is weighed according to molar ratio Ti:Nb=1:2, is passed through
After ball milling 10 hours, it is sintered 12 hours in 1100 DEG C of air, after sintered material is ground, using resistance meter
The resistance of powder is tested, test powder resistance is 2.3K Ω；Powder is prepared into electrode, electrode preparation method is as follows: taking 90%
Titanium niobium oxide, 5% Super_P conductive agent, 5130 binder of Solef of 5% Su Wei and NMP as solvent, this 4
After mixing, be applied as single side surface density is 150g/m to kind material2Electrode, be made into the button cell of model 2032, gold
Belong to cathode of the lithium piece as battery, the gram volume for testing button cell plays and high rate performance, charging/discharging voltage range for 1V~
3V；It is 152mAh/g that the gram volume that this material is tested at 0.2C, which plays,；Room temperature 10C multiplying power discharge capacity is 25.84mAh/
G, discharging efficiency 17%；It is therefore seen that individual TiNb2O7Do cell positive material, when the output power of battery, battery
Discharge capacity be greatly lowered.
To solve the above problems, the present invention provides a kind of graphene coated titanium niobium oxide combination electrode material, including
TiNbxO(2+2.5x)Kernel and graphene coated layer, the mass fraction of graphene coated layer are 0.01%-5%, wherein x 1.8-
2.3。TiNbxO(2+2.5x)With good lithium storage content and preferable security performance, but it is almost insulator, and conductivity is low,
And graphene has good conductivity, therefore by graphene and TiNbxO(2+2.5x)It is compound that the preferable class graphite of conductivity can be obtained
The TiNb of alkene doping and claddingxO(2+2.5x)Combination electrode material can improve the performance of electrode material charge and discharge, improve big output work
The discharge capacity of battery when rate.Wherein, covering amount is lower than 0.01%, and high current high rate performance can reduce, and covering amount is greater than 5%,
Capacity performance can be reduced.X can cause titanium niobium oxide structure imperfect less than 1.8 and greater than 2.3, and capacity plays low.
Preferably, the mass fraction of graphene coated layer is 0.1%-2%.
Preferably, x 1.9-2.0.
Above-mentioned graphene coated titanium niobium oxide combination electrode material is prepared it is a further object of the present invention to provide a kind of
Method, comprising:
Sintering after titanium source and the mixing of niobium source is obtained TiNb by the first stepxO(2+2.5x)Material, it is preferred that titanium source is rubbed with niobium source
You are than being Ti:Nb=1:1.5-1:2.5；
Second step, by TiNb obtained by the first stepxO(2+2.5x)Material is sintered after mixing with graphene or graphene presoma
To graphene coated titanium niobium oxide combination electrode material.
Wherein, titanium source, which refers to, can occur the change that solid phase reaction generates titanium niobium oxide with niobium source at high temperature containing titanium atom
Close object, can be organic titanium source, or inorganic ti sources, in technical solution, it is preferred that titanium source be metatitanic acid, titanium dioxide,
One of butyl titanate, isopropyl titanate and titanium oxyoxalate or a variety of combinations, it is furthermore preferred that titanium dioxide is Detitanium-ore-type
Titanium dioxide or rutile titanium dioxide.
Wherein, niobium source, which refers to, can occur the change that solid phase reaction generates titanium niobium oxide with titanium source at high temperature containing niobium atom
Object is closed, can be organic niobium source, or inorganic niobium source, in technical solution, it is preferred that niobium source is niobium oxalate, niobic acid and five
Aoxidize one of two niobiums or a variety of combinations.
In technical solution, it is preferred that the sintering temperature in the first step is 800 DEG C -1500 DEG C, and temperature can go out lower than 800 DEG C
Not exclusively, there are still the oxide of titanyl compound and niobium that solid phase reaction does not occur partially in product, temperature is higher than for now reaction
After 1500 DEG C, the TiNb that is preparedxO(2+2.5x)It is easy to happen melting, leads to TiNbxO(2+2.5x)Particle is excessive, is unfavorable for performance
Performance；It is furthermore preferred that the sintering temperature in the first step is 1000 DEG C -1400 DEG C.
In the first step, it is preferred that sintering atmosphere is one of air, oxygen or its mixing.
In technical solution, it is preferred that the sintering temperature in second step is 400 DEG C -1000 DEG C, and sintering temperature is lower than 400 DEG C,
Graphene cannot be uniformly coated on TiNbxO(2+2.5x)Surface, sintering temperature, which is higher than 1000 DEG C, can make TiNbxO(2+2.5x)Particle is long
Greatly, it is unfavorable for performance performance, it is furthermore preferred that the sintering temperature in second step is 500 DEG C -800 DEG C.
In technical solution, it is preferred that second step includes: by the resulting TiNb of the first stepxO(2+2.5x)Material and graphene are mixed
Close, and carry out grinding both make mixing more evenly, by spraying to preliminarily form the particle of certain particle size, be then sintered, obtain
Graphene coated titanium niobium oxide combination electrode material.Wherein, lapping mode can be wet grinding or dry grinding.
In technical solution, it is preferred that in second step, the partial size D50 of the particle obtained after grinding is 0.001 μm -5 μm, excellent
Choosing, the partial size D50 of the particle obtained after grinding is 0.05 μm -1 μm.
In technical solution, it is preferred that in second step, the partial size D50 of the particle obtained after spraying is 4-50 μm, it is preferred that
The partial size D50 of the particle obtained after spraying is 8-20 μm.
Another object of the present invention is to provide a kind of lithium primary battery, and lithium primary battery is with above-mentioned graphene coated titanium niobium
Oxide combination electrode material is positive electrode active materials, using lithium as negative electrode active material.It is aoxidized using the titanium niobium of graphene coated
Object TiNbxO(2+2.5x)Lithium primary battery as a positive electrode active material, theoretical capacity are high；Titanium niobium oxide TiNbxO(2+2.5x)
Belong to " shear surface ReO3 structure ", this structure is more suitable for the insertion and abjection of lithium ion, and its space structure than simple ReO3
Substantially it does not change, therefore it is safer in process of intercalation.Simultaneously as its special structure and using graphene coated
Mode makes it have the high current pulsed discharge characteristic that other lithium primary battery does not have.
In technical solution, it is preferred that lithium primary battery is button, cylindrical type, square or Soft Roll formula battery.
It is yet another object of the invention to provide the methods for preparing above-mentioned lithium primary battery, including successively carry out: preparing positive and negative
Pole slurry；Coating sizing-agent；It rolls；Punching；Baking；Fluid injection.
The specific embodiment of the invention is described further below with reference to several embodiments:
Embodiment one
Graphene coated titanium niobium oxide combination electrode material described in the present embodiment, including TiNb2O7Kernel and graphene
Clad, graphene coated layer mass fraction are 1%.It is specific the preparation method is as follows:
Titanium dioxide 23.42g and the 76.58g niobium pentaoxide of Detitanium-ore-type is weighed according to molar ratio Ti:Nb=1:2, is passed through
After ball milling 10 hours, it is sintered in 1100 DEG C of air 12 hours, then by the titanium niobium oxide of generation and graphene powder (content
1%) after ball milling 10 hours, it is sintered 4h under 750 DEG C of nitrogen atmosphere, after then grinding sintered material, uses
Resistance meter tests the resistance of powder, and test powder resistance is 80 Ω；Powder is prepared into electrode, electrode preparation method is such as
Under: take 90% titanium niobium oxide, 5% Super_P conductive agent, 5130 binder of Solef of 5% Su Wei and NMP as
Solvent, after mixing, be applied as single side surface density is 150g/m to this 4 kinds of materials2Electrode, and rolled, be punched, being toasted,
Fluid injection etc. is made into the button cell of model 2032, and cathode of the metal lithium sheet as battery tests the gram volume hair of button cell
It waves and high rate performance, charging/discharging voltage range is 1V~3V；It is 259mAh/g that the gram volume that this material is tested at 0.2C, which plays,；
Room temperature 10C multiplying power discharge capacity is 249mAh/g, discharging efficiency 96.14%.The electrode material has excellent gram volume
And high rate performance, the lithium primary battery energy density is high, and high safety and reliability has heavy current pulse characteristic.
Embodiment two
Graphene coated titanium niobium oxide combination electrode material described in the present embodiment, including TiNb1.9O6.75Kernel and stone
Black alkene clad, graphene coated layer mass fraction are 0.8%.It is specific the preparation method is as follows:
Titanium dioxide 23.42g and the 76.58g niobium pentaoxide of Detitanium-ore-type is weighed according to molar ratio Ti:Nb=1:2, is passed through
After ball milling 10 hours, it is sintered in 1000 DEG C of air 12 hours, then by the titanium niobium oxide of generation and graphene powder (content
0.8%) after ball milling 10 hours, it is sintered 4h under 750 DEG C of nitrogen atmosphere, after then grinding sintered material, adopts
With the resistance of resistance meter test powder, test powder resistance is 103 Ω；Powder is prepared into electrode, electrode preparation method
It is as follows: 90% titanium niobium oxide, 5% Super_P conductive agent, 5130 binder of Solef of 5% Su Wei and NMP being taken to do
For solvent, after mixing, be applied as single side surface density is 150g/m to this 4 kinds of materials2Electrode, and rolled, be punched, dried
Roasting, fluid injection etc. is made into the button cell of model 2032, and cathode of the metal lithium sheet as battery tests the gram volume of button cell
It plays and high rate performance, charging/discharging voltage range is 1V~3V；It is 243mAh/ that the gram volume that this material is tested at 0.2C, which plays,
g；Room temperature 10C multiplying power discharge capacity is 211.5mAh/g, discharging efficiency 87.04%.The electrode material has excellent gram
Capacity and high rate performance, the lithium primary battery energy density is high, and high safety and reliability has heavy current pulse characteristic.
Embodiment three
Graphene coated titanium niobium oxide combination electrode material described in the present embodiment, including TiNb2O7Kernel and graphene
Clad, graphene coated layer mass fraction are 1.2%.It is specific the preparation method is as follows:
Titanium dioxide 23.42g and the 76.58g niobium pentaoxide of Detitanium-ore-type is weighed according to molar ratio Ti:Nb=1:2, is passed through
After ball milling 10 hours, it is sintered in 1200 DEG C of air 12 hours, then by the titanium niobium oxide of generation and graphene powder (content
1.2%) after ball milling 10 hours, it is sintered 4h under 750 DEG C of nitrogen atmosphere, after then grinding sintered material, adopts
With the resistance of resistance meter test powder, test powder resistance is 70 Ω；Powder is prepared into electrode, electrode preparation method is such as
Under: take 90% titanium niobium oxide, 5% Super_P conductive agent, 5130 binder of Solef of 5% Su Wei and NMP as
Solvent, after mixing, be applied as single side surface density is 150g/m to this 4 kinds of materials2Electrode, and rolled, be punched, being toasted,
Fluid injection etc. is made into the button cell of model 2032, and cathode of the metal lithium sheet as battery tests the gram volume hair of button cell
It waves and high rate performance, charging/discharging voltage range is 1V~3V；It is 246mAh/g that the gram volume that this material is tested at 0.2C, which plays,；
Room temperature 10C multiplying power discharge capacity is 241mAh/g, discharging efficiency 98%.The electrode material is with excellent gram volume and again
Rate performance, the lithium primary battery energy density is high, and high safety and reliability has heavy current pulse characteristic.
Example IV
Graphene coated titanium niobium oxide combination electrode material described in the present embodiment, including TiNb2O7Kernel and graphene
Clad, graphene coated layer mass fraction are 1%.It is specific the preparation method is as follows:
A certain amount of Detitanium-ore-type metatitanic acid and niobic acid are weighed according to molar ratio Ti:Nb=1:2, after ball milling 10 hours,
It is sintered in 1100 DEG C of air 12 hours, it is then that the titanium niobium oxide of generation and graphene powder (content 1%) ball milling 10 is small
Shi Hou is sintered 4h under 750 DEG C of nitrogen atmosphere, after then grinding sintered material, is surveyed using resistance meter
The resistance of powder is tried, test powder resistance is 78 Ω；Powder is prepared into electrode, electrode preparation method is as follows: taking 90% titanium
Niobium oxide, 5% Super_P conductive agent, 5130 binder of Solef of 5% Su Wei and NMP are as solvent, this 4 kinds of objects
After mixing, be applied as single side surface density is 150g/m to material2Electrode, and rolled, be punched, being toasted, fluid injection etc. be made into it is soft
The gram volume of packet laminated batteries, cathode of the metal lithium sheet as battery, test Soft Roll laminated batteries plays and high rate performance, charge and discharge
Piezoelectric voltage range is 1V~3V；It is 262mAh/g that the gram volume that this material is tested at 0.2C, which plays,；It discharges under room temperature 10C multiplying power
Capacity is 253mAh/g, discharging efficiency 96.56%.The electrode material has excellent gram volume and high rate performance, the lithium one
Primary cell energy density is high, and high safety and reliability has heavy current pulse characteristic.
Embodiment five
Graphene coated titanium niobium oxide combination electrode material described in the present embodiment, including TiNb2O7Kernel and graphene
Clad, graphene coated layer mass fraction are 1%.It is specific the preparation method is as follows:
Titanium dioxide 23.42g and the 76.58g niobium pentaoxide of Detitanium-ore-type is weighed according to molar ratio Ti:Nb=1:2, is passed through
After ball milling 10 hours, it is sintered in 1100 DEG C of air 12 hours, then by the titanium niobium oxide of generation and sucrose ball milling 10 hours
Afterwards, it is sintered 4h under 750 DEG C of nitrogen atmosphere, after then grinding sintered material, is tested using resistance meter
The resistance of powder, test powder resistance are 156 Ω；Powder is prepared into electrode, electrode preparation method is as follows: taking 90% titanium niobium
Oxide, 5% Super_P conductive agent, 5130 binder of Solef of 5% Su Wei and NMP are as solvent, slurry solid content
It is 46%, after mixing, be applied as single side surface density is 150g/m to this 4 kinds of materials2Electrode, and rolled, be punched, dried
Roasting, fluid injection etc. is made into cylindrical battery, and cathode of the metal lithium sheet as battery, the gram volume for testing button cell plays and multiplying power
Performance, charging/discharging voltage range are 1V~3V；It is 203mAh/g that the gram volume that this material is tested at 0.2C, which plays,；Room temperature 10C
Multiplying power discharge capacity is 172.5mAh/g, discharging efficiency 84.98%.The electrode material has excellent gram volume and multiplying power
Performance, the lithium primary battery energy density is high, and high safety and reliability has heavy current pulse characteristic.
Several embodiments of the present invention are described in detail above, but the content is only preferable implementation of the invention
Example, should not be considered as limiting the scope of the invention.It is all according to all the changes and improvements made by the present patent application range
Deng should still be within the scope of the patent of the present invention.
Claims (10)
1. a kind of graphene coated titanium niobium oxide combination electrode material, it is characterised in that: including TiNbxO(2+2.5x)Kernel and stone
Black alkene clad, the mass fraction of the graphene coated layer are 0.01%-5%, wherein x 1.8-2.3, it is preferred that described
The mass fraction of graphene coated layer is 0.1%-2%, it is preferred that x 1.9-2.0.
2. a kind of method for preparing graphene coated titanium niobium oxide combination electrode material as described in claim 1, feature
It is: includes:
Sintering after titanium source and the mixing of niobium source is obtained TiNb by the first stepxO(2+2.5x)Material, it is preferred that the titanium source and the niobium
Source molar ratio is Ti:Nb=1:1.5-1:2.5；
Second step, by TiNb obtained by the first stepxO(2+2.5x)Sintering obtains institute after material is mixed with graphene or graphene presoma
State graphene coated titanium niobium oxide combination electrode material.
3. the method for graphene coated titanium niobium oxide combination electrode material according to claim 2, it is characterised in that: institute
Stating titanium source is one of metatitanic acid, titanium dioxide, butyl titanate, isopropyl titanate and titanium oxyoxalate or a variety of combinations, excellent
Choosing, the titanium dioxide is the titanium dioxide or rutile titanium dioxide of Detitanium-ore-type.
4. the method for graphene coated titanium niobium oxide combination electrode material according to claim 2 or 3, feature exist
In: the niobium source is one of niobium oxalate, niobic acid and niobium pentaoxide or a variety of combinations.
5. according to the method for any graphene coated titanium niobium oxide combination electrode material of claim 2-4, feature
Be: the sintering temperature in the first step is 800 DEG C -1500 DEG C, it is preferred that the sintering temperature in the first step is 1000 DEG C -1400
℃。
6. according to the method for any graphene coated titanium niobium oxide combination electrode material of claim 2-5, feature
Be: the sintering temperature in second step is 400 DEG C -1000 DEG C, it is preferred that the sintering temperature in second step is 500 DEG C -800 DEG C.
7. according to the method for any graphene coated titanium niobium oxide combination electrode material of claim 2-6, feature
Be: second step includes: by the resulting TiNb of the first stepxO(2+2.5x)Material is mixed with graphene or graphene presoma, is gone forward side by side
Row grinds, is spraying, is then sintered, obtains the graphene coated titanium niobium oxide combination electrode material, it is preferred that grinding
The partial size D50 of the particle obtained afterwards is 0.001 μm -5 μm, it is furthermore preferred that the partial size D50 of the particle obtained after grinding is 0.05 μ
M-1 μm, it is preferred that the partial size D50 of the particle obtained after spraying is 4-50 μm, it is furthermore preferred that the grain of the particle obtained after spraying
Diameter D50 is 8-20 μm.
8. a kind of lithium primary battery, it is characterised in that: the lithium primary battery is with graphene coated titanium niobium described in claim 1
Oxide combination electrode material is positive electrode active materials, using lithium as negative electrode active material.
9. lithium primary battery according to claim 8, it is characterised in that: the lithium primary battery is button, cylindrical type, side
Type or Soft Roll formula battery.
10. the method for preparing lithium primary battery as claimed in claim 8 or 9, including successively carry out: prepare anode and cathode slurry；
Coating sizing-agent；It rolls；Punching；Baking；Fluid injection.
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