CN108649189A - Titanium carbide/carbon core-shell nano linear array load nitrogen-doped titanic acid lithium composite material and its preparation method and application - Google Patents
Titanium carbide/carbon core-shell nano linear array load nitrogen-doped titanic acid lithium composite material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of titanium carbide/carbon core-shell nano linear arrays to load nitrogen-doped titanic acid lithium composite material and its preparation method and application, and this method includes：Alundum (Al2O3) is grown in titanium net using technique for atomic layer deposition；Using chemical vapour deposition technique in titanium net growth titanium carbide/carbon core-shell nano line core shell array (TiC/C)；Titanium carbide/carbon core-shell nano linear array composite material is placed in solution and carries out hydro-thermal reaction again, is washed later, drying and calcination, obtains LTO@TiC/C；N LTO@TiC/C finally are obtained to LTO@TiC/C composite array nitratings using ammonia nitrating technology.The composite material of the structure has the cycle life of excellent high rate capability and overlength as lithium ion battery negative material.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, and in particular to a kind of titanium carbide/carbon core-shell nano line
Array-supported nitrogen-doped titanic acid lithium composite material and its preparation method and application.
Background technology
Since the 21th century, energy and environmental problem is increasingly serious, and the exploitation of green energy resource is also increasingly paid attention to.For
Realization high-energy conversion efficiency and energy density, development high-performance electric chemistry energy storage technology have become the emphasis studied now.
Lithium ion battery has many advantages, such as that energy density is high, has extended cycle life, memory-less effect, is widely used to portable electronic and sets
The fields such as standby (such as mobile phone, digital camera, video camera, laptop) and electric tool, and gradually to electrical salf-walking
The fields such as vehicle, electric vehicle, new energy energy storage are expanded.However, commercialized graphite cathode is because of low ion and electronics now
Efficiency of transmission can not meet this demand.Therefore, it is badly in need of developing a kind of lithium ion battery with super-quick charging discharge performance
Negative material.
In lithium ion battery negative material, compared with graphite cathode, with Li4Ti5O12For the battery safety of cathode
More preferably.Lithium titanate has the charge and discharge platform of 1.55V, it is possible to prevente effectively from the formation of SEI films and Li dendrite, improves safety
Energy.The storage lithium process of lithium titanate is to pass through Li4Ti5O12With Li7Ti5O12Between phase transition complete, theoretical capacity 175mAh
g-1.Cubical expansivity is only 0.2% during phase transition, so it is referred to as zero strain material, therefore it is steady with fabulous cycle
Qualitative and high rate capability.But lower electronic conductivity and ionic mobility limit its application under high current.
So how to improve the electronic conductivity of lithium titanate and ionic mobility is that it is applied urgently as lithium ion battery negative material
Key scientific problems to be solved.
Currently, by by lithium titanate nanosizing or with other conductive materials it is compound be improve its electronic conductivity and from
The effective way of transport factor.Conductive material generally compound with it is carbon material or the high material of other conductivity, especially
Array structure materials.These arrays provide a conducting matrix grain for lithium titanate, entire electrodic electron conductivity are improved, to change
Kind high rate capability.
Invention content
The object of the present invention is to provide a kind of titanium carbide/carbon core-shell nano linear array load nitrogen-doped titanic acid lithium is compound
Material and its preparation method and application when the electrode material is used for lithium ion battery negative material, has excellent high power forthright
Energy and cyclical stability.
A kind of preparation method of titanium carbide/carbon core-shell nano linear array load nitrogen-doped titanic acid lithium composite material, lithium titanate
Nanometer sheet is equably covered on titanium carbide/carbon nanocoils array, then, by ammonia nitrating, is obtained titanium carbide/carbon nucleocapsid and is received
Nanowire arrays load nitrogen-doped titanic acid lithium composite material.
The present invention by with titanium net load titanium carbide/carbon core-shell nano linear array (TiC/C) be conducting matrix grain, hydro-thermal method institute
Lithium titanate (the Li obtained4Ti5O12, LTO) and nanometer sheet is equably covered in titanium carbide/carbon core-shell nano linear array, pass through ammonia
Nitrating obtains N-LTO@TiC/C nucleocapsid array electrode materials, to the cycle life for obtaining overlength and excellent high rate capability.
A kind of preparation method of titanium carbide/carbon core-shell nano linear array load nitrogen-doped titanic acid lithium composite material, including with
Lower step：
(1) one layer of Al is grown in titanium net using atomic layer deposition (ALD) technology2O3, obtain load Al2O3Titanium net；
(2) chemical vapor deposition (CVD) technology is utilized to load Al obtained by step (1)2O3Titanium net on growth titanium carbide/
Carbon core-shell nano linear array obtains titanium carbide/carbon core-shell nano linear array combination electrode material；
(3) lithium hydroxide, hydrogen peroxide and isopropyl titanate are dissolved in water respectively, form solution A；
(4) titanium carbide obtained by step (2)/carbon core-shell nano linear array combination electrode material is placed in solution A, is carried out
Hydro-thermal reaction is washed, drying and calcination later, obtains titanium carbide/carbon core-shell nano linear array load lithium titanate
(Li4Ti5O12, LTO) and composite array structure, i.e. LTO@TiC/C；
(5) ammonia nitrating technology is utilized, LTO@TiC/C composite array electrodes obtained by step (4) are placed in tube furnace,
Under the atmosphere of ammonia, reaction obtains titanium carbide/carbon core-shell nano linear array load nitrogen-doped titanic acid lithium composite material, i.e. N-
LTO@TiC/C。
It is used as the preferred technical solution of the present invention below：
In step (1), Al2O3In deposition, the sources Al use Al (CH3), the sources O use H2O, reaction temperature are 200-300 DEG C.
In step (2), reaction atmosphere is the mixed gas that argon gas and hydrogen carry acetone steam, and the flow of argon gas is 100-
150sccm, the flow that hydrogen carries acetone steam are 10-20sccm, and reaction temperature and time are 800-900 DEG C and 1-3 respectively
Hour.
In step (3), the solution A uses the component of following ratio：
In step (4), hydro-thermal reaction is carried out at 120-140 DEG C 8-12 hours.Protective atmosphere is argon gas, reaction temperature when calcining
Degree is 500-700 DEG C, and the reaction time is 3-6 hours.
In step (5), the flow of ammonia is respectively 40-60sccm, and reaction temperature and time are respectively 300-500 DEG C and 1-
3 hours.
The titanium carbide/carbon core-shell nano linear array loads nitrogen-doped titanic acid lithium composite material, Li4Ti5O12Content is
1-3mg cm-2。
The titanium carbide/carbon core-shell nano linear array loads nitrogen-doped titanic acid lithium composite material, including titanium net, equably
Titanium carbide/carbon core-shell nano the line being grown in titanium net, and be equably covered on the titanium carbide/carbon core-shell nano line
Nitrogen-doped titanic acid lithium nanometer sheet, the titanium carbide/carbon core-shell nano line include：It is linear kernel with titanium carbide, is coated on
Shelly-shaped carbon is formed on the titanium carbide.
Titanium carbide/carbon core-shell nano linear array loads nitrogen-doped titanic acid lithium composite array particularly as negative electrode of lithium ion battery
Material cuts obtained N-LTO@TiC/C films as lithium ion cell electrode assembled battery into pieces.Diaphragm is micropore poly- third
Alkene film, electrolyte is to 1molL-1LiPF6For solute, volume ratio 1:1 ethylene carbonate (EC) and dimethyl carbonate (DMC)
For solvent, cathode is lithium piece, and battery assembles completion in the glove box full of argon gas.
The lithium ion battery that assembles carries out constant current charge-discharge test after placing 12 hours, charging/discharging voltage be 2.5V~
1.0V measures capacity, multiplying power property and the charge-discharge performance of negative electrode of lithium ion battery in 25 ± 1 DEG C of environment.
Compared with prior art, the invention has the advantages that：
(1) present invention is prepared for titanium carbide/carbon core using atomic layer deposition combination chemical vapour deposition technique in titanium net
Shell nano wire nucleocapsid array, ensure that nano wire is equably covered in substrate, and nanometer linear content can in forming process
Control.
(2) the TiC/C core-shell nano line core shell array large specific surface areas prepared by, provide more active sites and
Increase the contact area between electrode and electrolyte；Electric conductivity is high, to provide express passway for the transmission of electronics；Mechanicalness
Can be good, to ensure that performance of the electrode in cyclic process is stablized.
(3) the N-LTO@TiC/C composite materials prepared by, N doping improves lithium titanate oxygen vacancy concentration, to be conducive to
Ion is spread, and is increased electric conductivity, is improved the multiplying power and cycle performance of electrode material.
(4) the N-LTO@TiC/C prepared by are prepared into negative electrode of lithium ion battery, are the membrane electrode of self-supporting, directly cut
It cuts and can be used as electrode, eliminate the tedious steps of slurry preparation.
(5) the nucleocapsid array structure N-LTO@TiC/C lithium ion battery negative materials that the present invention prepares have super-high power
Rate performance (50C still has 67% theoretical capacity) and overlength cyclical stability (still have 99% initial appearance after 10000 cycles
Amount) the advantages that, there is superior application prospect in fast charging and discharging field.
Description of the drawings
Fig. 1 is that titanium carbide/carbon core-shell nano linear array prepared by embodiment 1 loads nitrogen-doped titanic acid lithium composite material
Process schematic, wherein (a) is the titanium carbide/carbon core-shell nano linear array (TiC/C) being grown in titanium net in Fig. 1, is (b)
Titanium carbide/carbon core-shell nano linear array load lithium titanate array structure (LTO TiC/C) (c) is titanium carbide/carbon core-shell nano line
Array-supported nitrogen-doped titanic acid lithium array structure (N-LTO@TiC/C)；
Fig. 2 is that the titanium carbide/carbon core-shell nano linear array prepared in embodiment 1 loads nitrogen-doped titanic acid lithium composite array electricity
The XRD spectrum of pole material；
Fig. 3 is that the SEM of (a) TiC/C arrays and (b) N-LTO@TiC/C arrays prepared in embodiment 1 schemes, wherein Fig. 3
(a) it is the SEM figures of the TiC/C arrays prepared in embodiment 1；Fig. 3 (b) is the N-LTO@TiC/C arrays prepared in embodiment 1
SEM schemes；
Fig. 4 is that the TEM of (a) TiC/C arrays and (b) N-LTO@TiC/C arrays prepared in embodiment 1 schemes, wherein Fig. 4
(a) it is the TEM figures of the TiC/C arrays prepared in embodiment 1, Fig. 4 (b) is the N-LTO@TiC/C arrays prepared in embodiment 1
TEM schemes；
Fig. 5 is that the titanium carbide/carbon core-shell nano linear array prepared in embodiment 1 loads nitrogen-doped titanic acid lithium composite array electricity
The battery high rate performance of pole material；
Fig. 6 is that the titanium carbide/carbon core-shell nano linear array prepared in embodiment 1 loads nitrogen-doped titanic acid lithium composite array electricity
The cycle performance of battery of pole material.
Specific implementation mode
The present invention is made below by embodiment and further being illustrated, but the invention is not limited in following realities
Example.
Embodiment 1
(1) one layer of Al is grown in titanium net using atomic layer deposition (ALD) technology2O3, the sources Al and the sources O are Al (CH respectively3)
And H2O, reaction temperature are 200 DEG C, obtain load Al2O3Titanium net.
(2) chemical vapor deposition (CVD) technology is utilized to load Al obtained by step (1)2O3Titanium net on growth titanium carbide/
Carbon core-shell nano linear array.Al will be loaded2O3Titanium net be placed in tube furnace, be passed through argon gas and hydrogen and carry the mixed of acetone steam
Gas is closed, the flow of argon gas is 100sccm, and the flow that hydrogen carries acetone steam is 10sccm, is reacted 1 hour at 800 DEG C,
TiC/C nano wire nucleocapsid arrays are formed, titanium carbide/carbon core-shell nano linear array combination electrode material is obtained.
(3) 0.9g lithium hydroxides, 2mL hydrogen peroxide and 1.2g isopropyl titanates are dissolved in 50mL water respectively, are formed
Solution A；
(4) titanium carbide obtained by step (2)/carbon core-shell nano linear array combination electrode material is placed in solution A,
Hydro-thermal reaction 8 hours at 120 DEG C are washed and dry later.Then, it is placed in the tube furnace of argon gas protection, at 500 DEG C at heat
Reason 3 hours obtains titanium carbide/carbon core-shell nano linear array load lithium titanate (Li4Ti5O12, LTO) and composite array structure, i.e.,
LTO@TiC/C；
(5) ammonia nitrating technology is utilized, LTO@TiC/C composite array electrodes obtained by step (4) are placed in tube furnace,
Under the atmosphere of 40sccm ammonias, 300 DEG C are reacted 1 hour, obtain titanium carbide/carbon core-shell nano linear array load nitrogen-doped titanic acid lithium
Composite array electrode material (i.e. titanium carbide/carbon core-shell nano linear array load nitrogen-doped titanic acid lithium composite material), i.e. N-LTO@
TiC/C。
(6) using N-LTO@TiC/C composite materials chip dryings obtained by step (5) as electrode material, diaphragm is poly- for micropore
Propylene film, electrolyte is to 1mol L-1LiPF6For solute, volume ratio 1:1 ethylene carbonate (EC) and dimethyl carbonate
(DMC) it is solvent, cathode is lithium piece, and battery assembles completion in the glove box full of argon gas.
It prepares titanium carbide/carbon nucleocapsid in conjunction with the method for atomic layer deposition, chemical vapor deposition, hydro-thermal and ammonia nitrating and receives
The preparation process that nanowire arrays load nitrogen-doped titanic acid lithium composite array electrode material is as shown in Figure 1, wherein (a) makes a living in Fig. 1
The TiC/C arrays in titanium net are grown, are (b) LTO@TiC/C arrays, are (c) N-LTO@TiC/C arrays.
Fig. 2 is the XRD spectrum that the present embodiment 1 prepares N-LTO@TiC/C composite materials.As seen from Figure 2 prepared by the present embodiment 1
N-LTO@TiC/C composite materials have lithium titanate (JCPDS 49-0207) characteristic peak and titanium carbide (JCPDS 65-8805)
Characteristic peak.Fig. 3 (a) is that the SEM of TiC/C nano wire nucleocapsid arrays schemes, and TiC/C core-shell nano lines are equably grown in titanium net
On.Fig. 3 (b) is N-LTO@TiC/C arrays, and the lithium titanate nanometer sheet of N doping is equably covered on TiC/C core-shell nano lines.
Fig. 4 (a) is that the TEM of TiC/C core-shell nano lines schemes, and can be clearly observed core (TiC) shell (C) structure of nano wire.Entirely
The diameter of nano wire is about 60nm, and wherein TiC is about 40nm, and carbon-coating is about 10nm.Fig. 4 (b) is N-LTO@TiC/C composite materials
TEM figures, it is observed that the diameter of composite material is about 500-600nm after load lithium titanate nanometer sheet.
Assembled lithium ion battery is subjected to constant current charge-discharge test, charging/discharging voltage section is 2.5V~1.0V.
Fig. 5 is the multiplying power figure of lithium ion battery, it can be seen from the figure that lithium ion battery in 1C, 2C, 5C, 10C, 20C, 30C, 40C and
Capacity is respectively 173mA h g under the current density of 50C-1、165mA h g-1、158mA h g-1、150mA h g-1、140mA h
g-1、131mA h g-1、124mA h g-1With 117mA h g-1, show excellent high rate performance.From the cycle performance figure of Fig. 6
As can be seen that lithium ion battery still has 99% capacity retention ratio, coulomb after being recycled 10000 times under the high current density of 10C
Efficiency maintains 99% or more, shows the cyclical stability of superelevation and the cycle life of overlength.
Embodiment 2
(1) one layer of Al is grown in titanium net using atomic layer deposition (ALD) technology2O3.The sources Al and the sources O are Al (CH respectively3)
And H2O, reaction temperature are 250 DEG C.
(2) chemical vapor deposition (CVD) technology is utilized to load Al obtained by step (1)2O3Titanium net on growth titanium carbide/
Carbon core-shell nano line core shell array.Al will be loaded2O3Titanium net be placed in tube furnace, be passed through argon gas and hydrogen and carry acetone steam
Mixed gas, the flow of argon gas is 130sccm, and the flow that hydrogen carries acetone steam is 15sccm, reacts 2 at 850 DEG C
Hour, obtain TiC/C core-shell nano line core shell arrays.
(3) 1g lithium hydroxides, 3mL hydrogen peroxide and 1.3g isopropyl titanates are dissolved in 60mL water respectively, are formed molten
Liquid A；
(4) titanium carbide obtained by step (2)/carbon core-shell nano linear array combination electrode material is placed in solution A,
Hydro-thermal reaction 10 hours at 130 DEG C are washed and dry later.Then, it is placed in the tube furnace of argon gas protection, it is hot at 600 DEG C
Processing 4 hours obtains titanium carbide/carbon core-shell nano linear array load lithium titanate (Li4Ti5O12, LTO) and composite array structure, i.e.,
LTO@TiC/C；
(5) ammonia nitrating technology is utilized, LTO@TiC/C composite array electrodes obtained by step (4) are placed in tube furnace,
Under the atmosphere of 50sccm ammonias, 400 DEG C are reacted 2 hours, obtain titanium carbide/carbon core-shell nano linear array load nitrogen-doped titanic acid lithium
Composite array electrode material, i.e. N-LTO@TiC/C.
(6) using N-LTO@TiC/C composite materials chip dryings obtained by step (5) as electrode material, diaphragm is poly- for micropore
Propylene film, electrolyte is to 1mol L-1LiPF6For solute, volume ratio 1:1 ethylene carbonate (EC) and dimethyl carbonate
(DMC) it is solvent, cathode is lithium piece, and battery assembles completion in the glove box full of argon gas.
Assembled lithium ion battery is subjected to constant current charge-discharge test, charging/discharging voltage section is 2.5V~1.0V.
Lithium ion battery capacity under the current density of 1C, 2C, 5C, 10C, 20C, 30C, 40C and 50C is respectively 171mA h g-1、
163mA h g-1、154mA h g-1、145mA h g-1、133mA h g-1、124mA h g-1、116mA h g-1With 106mA h
g-1, show excellent high rate performance.Lithium ion battery still has 95% after being recycled 10000 times under the high current density of 10C
Capacity retention ratio, coulombic efficiency maintain 99% or more, show the cyclical stability of superelevation and the cycle life of overlength.
Embodiment 3
(1) one layer of Al is grown in titanium net using atomic layer deposition (ALD) technology2O3.The sources Al and the sources O are Al (CH respectively3)
And H2O, reaction temperature are 300 DEG C.
(2) chemical vapor deposition (CVD) technology is utilized to load Al obtained by step (1)2O3Titanium net on growth titanium carbide/
Carbon nanocoils nucleocapsid array.Al will be loaded2O3Titanium net be placed in tube furnace, be passed through argon gas and hydrogen and carry the mixed of acetone steam
Gas is closed, the flow of argon gas is 150sccm, and the flow that hydrogen carries acetone steam is 20sccm, is reacted 3 hours at 900 DEG C,
Obtain TiC/C nano wire nucleocapsid arrays.
(3) 1.1g lithium hydroxides, 4mL hydrogen peroxide and 1.4g isopropyl titanates are dissolved in 70mL water respectively, are formed
Solution A；
(4) titanium carbide obtained by step (2)/carbon core-shell nano linear array combination electrode material is placed in solution A,
Hydro-thermal reaction 12 hours at 140 DEG C are washed and dry later.Then, it is placed in the tube furnace of argon gas protection, it is hot at 700 DEG C
Processing 6 hours obtains titanium carbide/carbon core-shell nano linear array load lithium titanate (Li4Ti5O12, LTO) and composite array structure, i.e.,
LTO@TiC/C；
(5) ammonia nitrating technology is utilized, LTO@TiC/C composite array electrodes obtained by step (4) are placed in tube furnace,
Under the atmosphere of 60sccm ammonias, 500 DEG C are reacted 3 hours, and it is compound to obtain the array-supported nitrogen-doped titanic acid lithium of titanium carbide/carbon nanocoils
Array electrode material, i.e. N-LTO@TiC/C.
(6) using N-LTO@TiC/C composite materials chip dryings obtained by step (5) as electrode material, diaphragm is poly- for micropore
Propylene film, electrolyte is to 1mol L-1LiPF6For solute, volume ratio 1:1 ethylene carbonate (EC) and dimethyl carbonate
(DMC) it is solvent, cathode is lithium piece, and battery assembles completion in the glove box full of argon gas.
Assembled lithium ion battery is subjected to constant current charge-discharge test, charging/discharging voltage section is 2.5V~1.0V.
Lithium ion battery capacity under the current density of 1C, 2C, 5C, 10C, 20C, 30C, 40C and 50C is respectively 170mA h g-1、
159mA h g-1、151mA h g-1、142mA h g-1、129mA h g-1、118mA h g-1、109mA h g-1With 101mA h
g-1, show excellent high rate performance.Lithium ion battery still has 93% after being recycled 10000 times under the high current density of 10C
Capacity retention ratio, coulombic efficiency maintain 99% or more, show the cyclical stability of superelevation and the cycle life of overlength.
A kind of titanium carbide/carbon core-shell nano linear array in Examples 1 to 3 loads nitrogen-doped titanic acid lithium composite array conduct
It is as shown in table 1 in maximum discharge capacity of the difference under current density after li-ion electrode materials are assembled into lithium ion battery：
Table 1
Claims (10)
1. a kind of preparation method of titanium carbide/carbon core-shell nano linear array load nitrogen-doped titanic acid lithium composite material, feature exist
In including the following steps：
(1) one layer of Al is grown in titanium net using technique for atomic layer deposition2O3, obtain load Al2O3Titanium net；
(2) chemical vapour deposition technique is utilized to load Al obtained by step (1)2O3Titanium net on growth titanium carbide/carbon core-shell nano
Linear array obtains titanium carbide/carbon core-shell nano linear array combination electrode material；
(3) lithium hydroxide, hydrogen peroxide and isopropyl titanate are dissolved in water respectively, form solution A；
(4) titanium carbide obtained by step (2)/carbon core-shell nano linear array combination electrode material is placed in solution A, carries out hydro-thermal
Reaction, is washed, drying and calcination later, obtains titanium carbide/carbon core-shell nano linear array load lithium titanate composite array knot
Structure, i.e. LTO@TiC/C；
(5) ammonia nitrating technology is utilized, LTO@TiC/C composite array electrodes obtained by step (4) are placed in tube furnace, in ammonia
Atmosphere under, reaction obtains titanium carbide/carbon core-shell nano linear array load nitrogen-doped titanic acid lithium composite material.
2. preparation method according to claim 1, which is characterized in that in step (1), Al2O3In deposition, the sources Al use Al
(CH3), the sources O use H2O, reaction temperature are 200-300 DEG C.
3. preparation method according to claim 1, which is characterized in that in step (2), reaction atmosphere is that argon gas and hydrogen are taken
The flow of mixed gas with acetone steam, argon gas is 100-150sccm, and the flow that hydrogen carries acetone steam is 10-
20sccm, reaction temperature and time are 800-900 DEG C and 1-3 hour respectively.
4. preparation method according to claim 1, which is characterized in that in step (3), the solution A uses to be compared below
The component of example：
5. preparation method according to claim 1, which is characterized in that in step (4), it is anti-that hydro-thermal is carried out at 120-140 DEG C
It answers 8-12 hours.
6. preparation method according to claim 1, which is characterized in that in step (4), protective atmosphere is argon gas when calcining,
Reaction temperature is 500-700 DEG C, and the reaction time is 3-6 hours.
7. preparation method according to claim 1, which is characterized in that in step (5), the flow of ammonia is respectively 40-
60sccm, reaction temperature and time are respectively 300-500 DEG C and 1-3 hour.
8. the titanium carbide prepared according to claim 1~7 any one of them preparation method/carbon core-shell nano linear array loads nitrogen
Doped lithium titanate composite material.
9. titanium carbide according to claim 8/carbon core-shell nano linear array loads nitrogen-doped titanic acid lithium composite material, special
Sign is, including titanium net, titanium carbide/carbon core-shell nano line for being equably grown in the titanium net, and is equably covered in
Nitrogen-doped titanic acid lithium nanometer sheet on the titanium carbide/carbon core-shell nano line；
The titanium carbide/carbon core-shell nano line includes：It is linear kernel with titanium carbide, is coated on the titanium carbide and is formed
Shelly-shaped carbon.
10. titanium carbide according to claim 8/carbon core-shell nano linear array loads nitrogen-doped titanic acid lithium composite material conduct
The application of lithium ion battery negative material.
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| CN111403718A (en) * | 2020-03-31 | 2020-07-10 | 浙江大学 | Titanium niobium oxide/vertical graphene/titanium carbide-carbon composite material and preparation method and application thereof |
| CN111410227A (en) * | 2020-03-25 | 2020-07-14 | 上海电力大学 | Lithium titanate negative electrode material and preparation method thereof |
| CN111490232A (en) * | 2019-01-25 | 2020-08-04 | 温州玖源锂电池科技发展有限公司 | Nitrogen-doped porous carbon pore channel loaded titanium nitride cathode material for lithium-sulfur battery and preparation method thereof |
| CN112551582A (en) * | 2020-12-10 | 2021-03-26 | 哈尔滨工业大学 | Preparation method and application of nitrogen-doped oxygen-deficient titanium niobate electrode material |
| CN113224293A (en) * | 2021-04-02 | 2021-08-06 | 湖北工程学院 | Preparation method and application of titanium carbide/carbon nano-film material |
| CN113636554A (en) * | 2021-08-12 | 2021-11-12 | 电子科技大学长三角研究院(湖州) | Titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material and preparation method and application thereof |
| CN113903912A (en) * | 2021-09-30 | 2022-01-07 | 常熟理工学院 | Preparation method of carbon-loaded titanium carbide material, product obtained by preparation method and application of product |
| CN115011971A (en) * | 2022-06-28 | 2022-09-06 | 刘优昌 | TiO 2 2 TiC/C electrocatalyst and preparation method thereof |
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| CN111490232A (en) * | 2019-01-25 | 2020-08-04 | 温州玖源锂电池科技发展有限公司 | Nitrogen-doped porous carbon pore channel loaded titanium nitride cathode material for lithium-sulfur battery and preparation method thereof |
| CN111410227A (en) * | 2020-03-25 | 2020-07-14 | 上海电力大学 | Lithium titanate negative electrode material and preparation method thereof |
| CN111410227B (en) * | 2020-03-25 | 2022-08-05 | 上海电力大学 | Lithium titanate negative electrode material and preparation method thereof |
| CN111403718A (en) * | 2020-03-31 | 2020-07-10 | 浙江大学 | Titanium niobium oxide/vertical graphene/titanium carbide-carbon composite material and preparation method and application thereof |
| CN111403718B (en) * | 2020-03-31 | 2021-06-15 | 浙江大学 | Titanium niobium oxide/vertical graphene/titanium carbide-carbon composite material and preparation method and application thereof |
| CN112551582A (en) * | 2020-12-10 | 2021-03-26 | 哈尔滨工业大学 | Preparation method and application of nitrogen-doped oxygen-deficient titanium niobate electrode material |
| CN113224293A (en) * | 2021-04-02 | 2021-08-06 | 湖北工程学院 | Preparation method and application of titanium carbide/carbon nano-film material |
| CN113636554A (en) * | 2021-08-12 | 2021-11-12 | 电子科技大学长三角研究院(湖州) | Titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material and preparation method and application thereof |
| CN113636554B (en) * | 2021-08-12 | 2022-12-20 | 电子科技大学长三角研究院(湖州) | Titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material and preparation method and application thereof |
| CN113903912A (en) * | 2021-09-30 | 2022-01-07 | 常熟理工学院 | Preparation method of carbon-loaded titanium carbide material, product obtained by preparation method and application of product |
| CN115011971A (en) * | 2022-06-28 | 2022-09-06 | 刘优昌 | TiO 2 2 TiC/C electrocatalyst and preparation method thereof |
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