CN108649189B - Titanium carbide/carbon core-shell nanowire array loaded nitrogen-doped lithium titanate composite material and preparation method and application thereof - Google Patents
Titanium carbide/carbon core-shell nanowire array loaded nitrogen-doped lithium titanate composite material and preparation method and application thereof Download PDFInfo
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000011258 core-shell material Substances 0.000 title claims abstract description 74
- 239000002070 nanowire Substances 0.000 title claims abstract description 72
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 66
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 27
- 238000005516 engineering process Methods 0.000 claims abstract description 16
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 12
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 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 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000002055 nanoplate Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 239000010406 cathode material Substances 0.000 abstract description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 description 19
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- 229910009866 Ti5O12 Inorganic materials 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000002135 nanosheet Substances 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910011229 Li7Ti5O12 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Abstract
The invention discloses a titanium carbide/carbon core-shell nanowire array loaded nitrogen-doped lithium titanate composite material as well as a preparation method and application thereof, wherein the method comprises the following steps: growing aluminum oxide on the titanium mesh by utilizing an atomic layer deposition technology; growing a titanium carbide/carbon core-shell nanowire core-shell array (TiC/C) on a titanium mesh by using a chemical vapor deposition technology; then placing the titanium carbide/carbon core shell nanowire array composite material in a solution for hydrothermal reaction, and then washing, drying and calcining to obtain LTO @ TiC/C; and finally, carrying out nitrogen doping on the LTO @ TiC/C composite array by utilizing an ammonia nitrogen doping technology to obtain N-LTO @ TiC/C. The constructed composite material has excellent high rate performance and ultra-long cycle life when being used as a lithium ion battery cathode material.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a titanium carbide/carbon core shell nanowire array loaded nitrogen-doped lithium titanate composite material and a preparation method and application thereof.
Background
Since the 21 st century, energy and environmental problems have become more serious, and development of green energy has been paid more attention. In order to achieve high energy conversion efficiency and energy density, the development of high-performance electrochemical energy storage technology has become the focus of current research. Lithium ion batteries have the advantages of high energy density, long cycle life, no memory effect, and the like, have been widely used in the fields of portable electronic devices (such as mobile phones, digital cameras, video cameras, notebook computers, and the like) and electric tools, and have been gradually expanded to the fields of electric bicycles, electric automobiles, new energy storage, and the like. However, the graphite negative electrodes now commercialized cannot meet this demand because of low ion and electron transport efficiency. Therefore, it is urgently needed to develop a lithium ion battery negative electrode material with ultra-fast charge and discharge performance.
In the lithium ion battery negative electrode material, compared with a graphite negative electrode, Li is used4Ti5O12The battery with the negative electrode has better safety performance. Lithium titanate has a charge-discharge platform of 1.55V, can effectively avoid the formation of SEI film and lithium dendrite, improves the security performance. The lithium storage process of the lithium titanate is performed by Li4Ti5O12With Li7Ti5O12The phase transition between the two is completed, and the theoretical capacity is 175mAh g-1. The volume expansion rate in the phase transition process is only 0.2%, so the material is called a zero-strain material, and has excellent cycle stability and high rate performance. However, the low electronic conductivity and ionic mobility limit their application at high currents. Therefore, how to improve the electronic conductivity and the ion mobility of lithium titanate is a key scientific problem to be solved urgently when the lithium titanate is used as a negative electrode material of a lithium ion battery.
At present, the nano-crystallization of lithium titanate or the compounding of lithium titanate and other conductive materials is an effective way for improving the electronic conductivity and the ionic mobility of lithium titanate. The conductive material compounded with the carbon material is carbon material or other material with high conductivity, especially array structure material. These arrays provide a conductive framework for lithium titanate, increasing the overall electrode electron conductivity, thereby improving high rate performance.
Disclosure of Invention
The invention aims to provide a titanium carbide/carbon core-shell nanowire array loaded nitrogen-doped lithium titanate composite material, and a preparation method and application thereof.
A preparation method of a titanium carbide/carbon core shell nanowire array loaded nitrogen-doped lithium titanate composite material comprises the steps of uniformly covering a titanium carbide/carbon nanowire array with lithium titanate nanosheets, and then carrying out nitrogen doping through ammonia gas to obtain the titanium carbide/carbon core shell nanowire array loaded nitrogen-doped lithium titanate composite material.
The lithium titanate (Li) obtained by a hydrothermal method by taking a titanium mesh loaded titanium carbide/carbon core-shell nanowire array (TiC/C) as a conductive framework4Ti5O12LTO) nanosheets are uniformly covered on the titanium carbide/carbon core-shell nanowire array, and the N-LTO @ TiC/C core-shell array electrode material is obtained by ammonia nitrogen doping, so that the ultra-long cycle life and the excellent high-rate performance are obtained.
A preparation method of a titanium carbide/carbon core shell nanowire array loaded nitrogen-doped lithium titanate composite material comprises the following steps:
(1) growing a layer of Al on a titanium mesh using Atomic Layer Deposition (ALD)2O3To obtain loaded Al2O3The titanium mesh of (2);
(2) carrying Al obtained in the step (1) by using a Chemical Vapor Deposition (CVD) technology2O3Growing a titanium carbide/carbon core-shell nanowire array on the titanium mesh to obtain a titanium carbide/carbon core-shell nanowire array composite electrode material;
(3) respectively dissolving lithium hydroxide, hydrogen peroxide and isopropyl titanate in water to form a solution A;
(4) placing the titanium carbide/carbon core-shell nanowire array composite electrode material obtained in the step (2) in a solution A for hydrothermal reaction, and then washing, drying and calcining to obtain titanium carbide/carbon core-shell nanowire array loaded lithium titanate (Li)4Ti5O12LTO) composite array structure, i.e., LTO @ TiC/C;
(5) and (3) placing the LTO @ TiC/C composite array electrode obtained in the step (4) into a tube furnace by using an ammonia nitrogen doping technology, and reacting in the atmosphere of ammonia gas to obtain the titanium carbide/carbon core-shell nanowire array loaded nitrogen doped lithium titanate composite material, namely N-LTO @ TiC/C.
The following are preferred technical schemes of the invention:
in step (1), Al2O3In the deposition, Al (CH) is used as an Al source3) O source is H2O, the reaction temperature is 200-300 ℃.
In the step (2), the reaction atmosphere is a mixed gas of argon and hydrogen carrying acetone vapor, the flow rate of argon is 100-150sccm, the flow rate of hydrogen carrying acetone vapor is 10-20sccm, and the reaction temperature and time are 800-900 ℃ and 1-3 hours, respectively.
In the step (3), the solution A adopts the following components in proportion:
in the step (4), the hydrothermal reaction is carried out at the temperature of 120-140 ℃ for 8-12 hours. During calcination, the protective atmosphere is argon, the reaction temperature is 500-700 ℃, and the reaction time is 3-6 hours.
In the step (5), the flow rate of ammonia gas is 40-60sccm, and the reaction temperature and time are 300-500 ℃ and 1-3 hours, respectively.
The titanium carbide/carbon core-shell nanowire array loaded nitrogen-doped lithium titanate composite material is Li4Ti5O12The content is 1-3mg cm-2。
The titanium carbide/carbon core-shell nanowire array loaded nitrogen-doped lithium titanate composite material comprises a titanium net, titanium carbide/carbon core-shell nanowires uniformly growing on the titanium net, and nitrogen-doped lithium titanate nanosheets uniformly covering the titanium carbide/carbon core-shell nanowires, wherein the titanium carbide/carbon core-shell nanowires comprise: the titanium carbide is taken as a linear inner core, and the titanium carbide is coated with the inner core to form shell-shaped carbon.
The titanium carbide/carbon core-shell nanowire array loaded nitrogen-doped lithium titanate composite array is particularly used as a lithium ion battery cathode material, and the obtained N-LTO @ TiC/C film is cut into small pieces to be used as a lithium ion battery electrode assembly battery. The diaphragm is a microporous polypropylene film, and the electrolyte is 1mol L-1LiPF6The battery is prepared by using Ethylene Carbonate (EC) and dimethyl carbonate (DMC) with a volume ratio of 1:1 as solvents and using a lithium sheet as a negative electrode in a glove box filled with argon.
And (3) standing the assembled lithium ion battery for 12 hours, carrying out constant current charge and discharge test, wherein the charge and discharge voltage is 2.5V-1.0V, and measuring the capacity, rate characteristics and charge and discharge cycle performance of the negative electrode of the lithium ion battery in an environment of 25 +/-1 ℃.
Compared with the prior art, the invention has the following advantages:
(1) the invention adopts the atomic layer deposition combined with the chemical vapor deposition technology to prepare the titanium carbide/carbon core-shell nanowire core-shell array on the titanium mesh, ensures that the nanowires uniformly cover the substrate, and has controllable nanowire dimension in the forming process.
(2) The prepared TiC/C core-shell nanowire core-shell array has large specific surface area, provides more active sites and increases the contact area between an electrode and electrolyte; the conductivity is high, so that a fast channel is provided for the transmission of electrons; the mechanical property is good, thereby ensuring the stable performance of the electrode in the circulating process.
(3) The N-LTO @ TiC/C composite material prepared by the method has the advantages that nitrogen doping improves the concentration of lithium titanate oxygen vacancies, so that ion diffusion is facilitated, the conductivity is improved, and the multiplying power and the cycle performance of an electrode material are improved.
(4) The prepared N-LTO @ TiC/C is prepared into a lithium ion battery cathode which is a self-supporting film electrode, and the cathode can be used as an electrode by directly shearing, so that the complicated step of slurry preparation is omitted.
(5) The N-LTO @ TiC/C lithium ion battery cathode material with the core-shell array structure, which is prepared by the invention, has the advantages of ultrahigh rate performance (67% of theoretical capacity still exists at 50C) and overlong cycle stability (99% of initial capacity still exists after 10000 cycles), and the like, and has excellent application prospects in the field of rapid charge and discharge.
Drawings
Fig. 1 is a schematic process diagram of a titanium carbide/carbon core shell nanowire array loaded nitrogen-doped lithium titanate composite material prepared in example 1, wherein in fig. 1, (a) is a titanium carbide/carbon core shell nanowire array (TiC/C) grown on a titanium mesh, (b) is a titanium carbide/carbon core shell nanowire array loaded lithium titanate array structure (LTO @ TiC/C), (C) is a titanium carbide/carbon core shell nanowire array loaded nitrogen-doped lithium titanate array structure (N-LTO @ TiC/C);
fig. 2 is an XRD spectrum of the titanium carbide/carbon core shell nanowire array supported nitrogen-doped lithium titanate composite array electrode material prepared in example 1;
FIG. 3 is an SEM image of (a) a TiC/C array and (b) an N-LTO @ TiC/C array prepared in example 1, wherein FIG. 3(a) is an SEM image of the TiC/C array prepared in example 1; FIG. 3(b) is an SEM image of the N-LTO @ TiC/C array prepared in example 1;
FIG. 4 is a TEM image of (a) a TiC/C array and (b) an N-LTO @ TiC/C array prepared in example 1, wherein FIG. 4(a) is a TEM image of the TiC/C array prepared in example 1, and FIG. 4(b) is a TEM image of the N-LTO @ TiC/C array prepared in example 1;
fig. 5 is a battery rate performance of the titanium carbide/carbon core shell nanowire array loaded nitrogen-doped lithium titanate composite array electrode material prepared in example 1;
fig. 6 shows the battery cycle performance of the titanium carbide/carbon core shell nanowire array loaded nitrogen-doped lithium titanate composite array electrode material prepared in example 1.
Detailed Description
The present invention will be further specifically described below by way of examples, but the present invention is not limited to the following examples.
Example 1
(1) Growing a layer of Al on a titanium mesh using Atomic Layer Deposition (ALD)2O3The Al source and the O source are each Al (CH)3) And H2O, the reaction temperature is 200 ℃, and the loaded Al is obtained2O3The titanium mesh of (1).
(2) Carrying Al obtained in the step (1) by using a Chemical Vapor Deposition (CVD) technology2O3Growing a titanium carbide/carbon core-shell nanowire array on the titanium mesh. Will carry Al2O3The titanium mesh is placed in a tubular furnace, mixed gas of argon and hydrogen carrying acetone vapor is introduced, the flow of the argon is 100sccm, the flow of the hydrogen carrying acetone vapor is 10sccm, and the reaction is carried out at 800 ℃ for 1 hour to form a TiC/C nanowire core-shell array, so that the titanium carbide/carbon core-shell nanowire array composite electrode material is obtained.
(3) Respectively dissolving 0.9g of lithium hydroxide, 2mL of hydrogen peroxide and 1.2g of isopropyl titanate in 50mL of water to form a solution A;
(4) and (3) placing the titanium carbide/carbon core-shell nanowire array composite electrode material obtained in the step (2) into the solution A, carrying out hydrothermal reaction for 8 hours at 120 ℃, and then washing and drying. Then, the mixture is placed in a tube furnace protected by argon, and is subjected to heat treatment at 500 ℃ for 3 hours to obtain the titanium carbide/carbon core-shell nanowire array loaded lithium titanate (Li)4Ti5O12LTO) composite array structure, i.e., LTO @ TiC/C;
(5) and (3) placing the LTO @ TiC/C composite array electrode obtained in the step (4) into a tubular furnace by using an ammonia gas nitrogen doping technology, and reacting for 1 hour at 300 ℃ in the atmosphere of 40sccm ammonia gas to obtain the titanium carbide/carbon core shell nanowire array loaded nitrogen-doped lithium titanate composite array electrode material (namely the titanium carbide/carbon core shell nanowire array loaded nitrogen-doped lithium titanate composite material), namely N-LTO @ TiC/C.
(6) Drying the N-LTO @ TiC/C composite material slices obtained in the step (5) to be used as an electrode material, wherein a diaphragm is a microporous polypropylene film, and 1mol L of electrolyte is used-1LiPF6The battery is prepared by using Ethylene Carbonate (EC) and dimethyl carbonate (DMC) with a volume ratio of 1:1 as solvents and using a lithium sheet as a negative electrode in a glove box filled with argon.
The preparation process of the titanium carbide/carbon core shell nanowire array loaded nitrogen-doped lithium titanate composite array electrode material prepared by combining atomic layer deposition, chemical vapor deposition, hydrothermal method and ammonia nitrogen doping method is shown in fig. 1, wherein in fig. 1, (a) is a TiC/C array growing on a titanium net, (b) is an LTO @ TiC/C array, and (C) is an N-LTO @ TiC/C array.
FIG. 2 is an XRD pattern of the N-LTO @ TiC/C composite material prepared in example 1. It can be seen from FIG. 2 that the N-LTO @ TiC/C composite material prepared in this example 1 has the characteristic peak of lithium titanate (JCPDS 49-0207) and the characteristic peak of titanium carbide (JCPDS 65-8805). FIG. 3(a) is an SEM image of a TiC/C nanowire core-shell array, with TiC/C core-shell nanowires uniformly grown on a titanium mesh. FIG. 3(b) is an N-LTO @ TiC/C array, with nitrogen-doped lithium titanate nano-sheets uniformly covering the TiC/C core-shell nanowires. Fig. 4(a) is a TEM image of a TiC/C core-shell nanowire, and the core (TiC) shell (C) structure of the nanowire can be clearly observed. The diameter of the whole nanowire is about 60nm, with TiC about 40nm and carbon layer about 10 nm. FIG. 4(b) is a TEM image of the N-LTO @ TiC/C composite material, and it can be observed that the diameter of the composite material after the lithium titanate nano-sheets are loaded is about 500-600 nm.
And carrying out constant current charge and discharge test on the assembled lithium ion battery, wherein the charge and discharge voltage interval is 2.5V-1.0V. FIG. 5 is a magnification chart of a lithium ion battery, and it can be seen from the graph that the capacity of the lithium ion battery is 173mA h g at current densities of 1C, 2C, 5C, 10C, 20C, 30C, 40C and 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-1And 117mA h g-1And excellent rate performance is shown. As can be seen from the cycle performance diagram of fig. 6, the lithium ion battery still has a capacity retention rate of 99% after being cycled 10000 times at a high current density of 10C, and the coulombic efficiency is maintained above 99%, which shows an ultra-high cycle stability and an ultra-long cycle life.
Example 2
(1) Growing a layer of Al on a titanium mesh using Atomic Layer Deposition (ALD)2O3. The Al source and the O source are each Al (CH)3) And H2O, the reaction temperature is 250 ℃.
(2) Carrying Al obtained in the step (1) by using a Chemical Vapor Deposition (CVD) technology2O3Growing a titanium carbide/carbon core-shell nanowire core-shell array on the titanium mesh. Will carry Al2O3The titanium mesh is placed in a tubular furnace, mixed gas of argon and hydrogen carrying acetone vapor is introduced, the flow of the argon is 130sccm, the flow of the hydrogen carrying acetone vapor is 15sccm, and the reaction is carried out for 2 hours at 850 ℃ to obtain the TiC/C core-shell nanowire core-shell array.
(3) Respectively dissolving 1g of lithium hydroxide, 3mL of hydrogen peroxide and 1.3g of isopropyl titanate in 60mL of water to form a solution A;
(4) and (3) placing the titanium carbide/carbon core-shell nanowire array composite electrode material obtained in the step (2) into the solution A, carrying out hydrothermal reaction for 10 hours at 130 ℃, and then washing and drying. Then, put under argon protectionHeat treating in a tube furnace at 600 deg.c for 4 hr to obtain nanometer lithium titanate loaded with titanium carbide/carbon core shell nanometer line array4Ti5O12LTO) composite array structure, i.e., LTO @ TiC/C;
(5) and (3) placing the LTO @ TiC/C composite array electrode obtained in the step (4) into a tubular furnace by utilizing an ammonia gas nitrogen doping technology, and reacting for 2 hours at 400 ℃ in the atmosphere of 50sccm ammonia gas to obtain the titanium carbide/carbon core shell nanowire array loaded nitrogen-doped lithium titanate composite array electrode material, namely N-LTO @ TiC/C.
(6) Drying the N-LTO @ TiC/C composite material slices obtained in the step (5) to be used as an electrode material, wherein a diaphragm is a microporous polypropylene film, and 1mol L of electrolyte is used-1LiPF6The battery is prepared by using Ethylene Carbonate (EC) and dimethyl carbonate (DMC) with a volume ratio of 1:1 as solvents and using a lithium sheet as a negative electrode in a glove box filled with argon.
And carrying out constant current charge and discharge test on the assembled lithium ion battery, wherein the charge and discharge voltage interval is 2.5V-1.0V. The capacity of the lithium ion battery is 171mA h g at current densities of 1C, 2C, 5C, 10C, 20C, 30C, 40C and 50C-1、163mA h g-1、154mA h g-1、145mA h g-1、133mA h g-1、124mA h g-1、116mA h g-1And 106mA h g-1And excellent rate performance is shown. The lithium ion battery still has a capacity retention rate of 95% after being cycled for 10000 times under a high current density of 10C, the coulombic efficiency is maintained above 99%, and the lithium ion battery has ultrahigh cycle stability and an overlong cycle life.
Example 3
(1) Growing a layer of Al on a titanium mesh using Atomic Layer Deposition (ALD)2O3. The Al source and the O source are each Al (CH)3) And H2O, the reaction temperature is 300 ℃.
(2) Carrying Al obtained in the step (1) by using a Chemical Vapor Deposition (CVD) technology2O3Growing a titanium carbide/carbon nanowire core-shell array on the titanium mesh. Will carry Al2O3The titanium net is arranged in a tubular furnace, mixed gas of argon and hydrogen carrying acetone vapor is introduced, and the flow of the argon isAnd (3) reacting at the temperature of 900 ℃ for 3 hours by using the hydrogen carrying acetone steam of which the flow rate is 20sccm at 150sccm to obtain the TiC/C nanowire core-shell array.
(3) Respectively dissolving 1.1g of lithium hydroxide, 4mL of hydrogen peroxide and 1.4g of isopropyl titanate in 70mL of water to form a solution A;
(4) and (3) placing the titanium carbide/carbon core-shell nanowire array composite electrode material obtained in the step (2) in the solution A, carrying out hydrothermal reaction at 140 ℃ for 12 hours, and then washing and drying. Then, placing the titanium carbide/carbon core-shell nanowire array in a tube furnace under the protection of argon, and carrying out heat treatment at 700 ℃ for 6 hours to obtain the titanium carbide/carbon core-shell nanowire array-loaded lithium titanate (Li)4Ti5O12LTO) composite array structure, i.e., LTO @ TiC/C;
(5) and (3) placing the LTO @ TiC/C composite array electrode obtained in the step (4) into a tubular furnace by using an ammonia gas nitrogen doping technology, and reacting for 3 hours at 500 ℃ in the atmosphere of 60sccm ammonia gas to obtain the titanium carbide/carbon nanowire array loaded nitrogen-doped lithium titanate composite array electrode material, namely N-LTO @ TiC/C.
(6) Drying the N-LTO @ TiC/C composite material slices obtained in the step (5) to be used as an electrode material, wherein a diaphragm is a microporous polypropylene film, and 1mol L of electrolyte is used-1LiPF6The battery is prepared by using Ethylene Carbonate (EC) and dimethyl carbonate (DMC) with a volume ratio of 1:1 as solvents and using a lithium sheet as a negative electrode in a glove box filled with argon.
And carrying out constant current charge and discharge test on the assembled lithium ion battery, wherein the charge and discharge voltage interval is 2.5V-1.0V. The capacity of the lithium ion battery is 170mA h g at the current density of 1C, 2C, 5C, 10C, 20C, 30C, 40C and 50C-1、159mA h g-1、151mA h g-1、142mA h g-1、129mA h g-1、118mA h g-1、109mA h g-1And 101mA h g-1And excellent rate performance is shown. The lithium ion battery still has 93 percent of capacity retention rate after being cycled for 10000 times under the high current density of 10C, the coulombic efficiency is maintained to be more than 99 percent, and the lithium ion battery has ultrahigh cycle stability and overlong cycle life.
The maximum discharge capacities of the titanium carbide/carbon core shell nanowire array loaded with the nitrogen-doped lithium titanate composite array as a lithium ion electrode material assembled into a lithium ion battery in the embodiments 1 to 3 under different current densities are shown in table 1:
TABLE 1
Claims (9)
1. A preparation method of a titanium carbide/carbon core shell nanowire array loaded nitrogen-doped lithium titanate composite material is characterized by comprising the following steps:
(1) growing a layer of Al on the titanium mesh by utilizing the atomic layer deposition technology2O3To obtain loaded Al2O3The titanium mesh of (2);
(2) carrying Al obtained in the step (1) by utilizing a chemical vapor deposition technology2O3Growing a titanium carbide/carbon core-shell nanowire array on the titanium mesh, wherein the reaction atmosphere is mixed gas of argon and hydrogen carrying acetone vapor, the flow of the argon is 100-150sccm, the flow of the hydrogen carrying acetone vapor is 10-20sccm, and the reaction temperature and the reaction time are respectively 800-900 ℃ and 1-3 hours, so as to obtain the titanium carbide/carbon core-shell nanowire array composite material;
(3) respectively dissolving lithium hydroxide, hydrogen peroxide and isopropyl titanate in water to form a solution A;
(4) placing the titanium carbide/carbon core-shell nanowire array composite material obtained in the step (2) in a solution A, carrying out hydrothermal reaction, and then washing, drying and calcining to obtain a titanium carbide/carbon core-shell nanowire array loaded lithium titanate composite array material, namely LTO @ TiC/C;
(5) and (3) placing the LTO @ TiC/C composite array material obtained in the step (4) into a tubular furnace by using an ammonia nitrogen doping technology, and reacting in the atmosphere of ammonia gas to obtain the titanium carbide/carbon core-shell nanowire array loaded nitrogen-doped lithium titanate composite material.
2. The method according to claim 1, wherein in the step (1), Al2O3In the depositionThe Al source is Al (CH)3)3O source is H2O, the reaction temperature is 200-300 ℃.
3. The method according to claim 1, wherein in the step (3), the solution A comprises the following components in proportion:
4. the preparation method as claimed in claim 1, wherein in the step (4), the hydrothermal reaction is carried out at 120-140 ℃ for 8-12 hours.
5. The method as claimed in claim 1, wherein in the step (4), the protective atmosphere during the calcination is argon, the reaction temperature is 500-700 ℃, and the reaction time is 3-6 hours.
6. The method as claimed in claim 1, wherein in the step (5), the flow rate of the ammonia gas is 40-60sccm, and the reaction temperature and time are 300-500 ℃ and 1-3 hours, respectively.
7. The titanium carbide/carbon core-shell nanowire array prepared by the preparation method of any one of claims 1 to 6 is loaded with a nitrogen-doped lithium titanate composite material.
8. The titanium carbide/carbon core shell nanowire array supported nitrogen-doped lithium titanate composite material of claim 7, comprising a titanium mesh, titanium carbide/carbon core shell nanowires uniformly grown on the titanium mesh, and nitrogen-doped lithium titanate nanoplates uniformly overlaid on the titanium carbide/carbon core shell nanowires;
the titanium carbide/carbon core-shell nanowire comprises: the titanium carbide is taken as a linear inner core, and the titanium carbide is coated with the inner core to form shell-shaped carbon.
9. The application of the titanium carbide/carbon core-shell nanowire array loaded nitrogen-doped lithium titanate composite material as a negative electrode material of a lithium ion battery according to claim 7.
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