CN116779877A - Preparation method and application of molybdenum nitride coated copper nanowire/foam copper current collector with lithium-philic gradient - Google Patents
Preparation method and application of molybdenum nitride coated copper nanowire/foam copper current collector with lithium-philic gradient Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 160
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- 230000008021 deposition Effects 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
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- 239000011733 molybdenum Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 7
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- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 5
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 45
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Abstract
A preparation method and application of a molybdenum nitride coated copper nanowire/foam copper current collector with a lithium-philic gradient relate to a preparation method and application of a foam copper current collector. The invention aims to solve the problems that lithium grows uncontrollably on the smooth surfaces of the existing foam copper serving as a three-dimensional current collector, the lithium affinity of copper is poor, the nucleation barrier on the surface of the lithium is high, the uniform nucleation of the lithium is further limited, and the growth of lithium dendrites is accelerated. The method comprises the following steps: 1. preparing a copper nanowire/foam copper composite material; 2. preparing MoN@CW@CF; use of a molybdenum nitride coated copper nanowire/copper foam current collector with a lithium-philic gradient on a lithium metal battery anode. The invention can obtain the molybdenum nitride coated copper nanowire/foam copper current collector with a lithium-philic gradient.
Description
Technical Field
The invention relates to a preparation method and application of a foamy copper current collector.
Background
Global energy crisis and unprecedented power consumption have prompted the development of sustainable power energy storage technologies, and high density rechargeable batteries have attracted increasing attention. Of all available solid anode materials, lithium metal has a very high theoretical specific capacity (3860 mAh g -1 ) And the lowest reduction potential (-3.04V vs. standard hydrogen electrode) are widely considered to be optimalOne of the anodes. However, practical application of lithium metal anodes also faces some challenges. In particular, non-uniform deposition of lithium, infinite volume change of lithium during electroplating/stripping, and formation of a fragile solid-electrolyte interface (SEI) layer. All of this results in the growth of lithium dendrites and the formation of "dead lithium" leading to serious safety problems for lithium metal batteries. In addition, irreversible consumption of lithium and electrolyte also results in low coulombic efficiency and shorter cycle life. In recent years, great efforts have been made to solve the above-mentioned problems of lithium metal anodes. Constructing a lithium metal anode with a three-dimensional body is an effective strategy to reduce local current density and volume effects during cycling. Common three-dimensional bulk conductive nanostructured current collectors, such as metal foams, copper nanowires, lithium-containing alloys, layered reduced graphene oxide, carbon nanospheres, carbon nanofibers, biochar frameworks, etc., are mostly focused on lithium deposition homogenization on planes parallel to the electrodes, while the vertical lithium ion concentration gradients present during cycling are usually ignored. In particular, in a three-dimensional body, the vertical lithium ion concentration has an adverse effect on uniform lithium deposition in the vertical direction. The lithium ions on the surface of the body generate higher lithium ion flux in the electrolyte, which weakens the effect of the three-dimensional structure, resulting in the blanket deposition of lithium and lithium dendrites. A more efficient and generalized strategy is developed to overcome the non-uniform vertical lithium deposition caused by the lithium ion concentration gradient, which is critical for the application of the three-dimensional body of the lithium metal battery.
Conventional Copper Foam (CF) is the preferred material compared to other three-dimensional current collectors. The primary copper foam frame can provide abundant micro-scale pores, can accommodate a large amount of lithium metal, and reduces volume expansion. However, the relatively smooth skeletal surface and lower surface area of CF does not provide good electrical contact for the circulating lithium, resulting in uncontrolled growth of lithium on these smooth surfaces. The secondary structure of the foam copper is reasonably designed, so that the volume expansion can be released, and the utilization rate of lithium is improved. In addition, copper has poor lithium affinity, so that the nucleation barrier on the surface of lithium is high, uniform nucleation of lithium is further limited, and growth of lithium dendrites is accelerated.
Disclosure of Invention
The invention aims to solve the problems that the existing foam copper is used as a three-dimensional current collector, lithium grows uncontrollably on the smooth surfaces, the lithium affinity of copper is poor, the nucleation barrier on the surface of the lithium is high, the uniform nucleation of the lithium is further limited, and the growth of lithium dendrites is accelerated, and provides a preparation method and application of a molybdenum nitride coated copper nanowire/foam copper current collector with a lithium affinity gradient.
The preparation method of the molybdenum nitride coated copper nanowire/foam copper current collector with the lithium-philic gradient comprises the following steps:
1. preparing a copper nanowire/foam copper composite material:
(1) copper foam is used as a working electrode, a platinum sheet is used as a counter electrode, potassium hydroxide solution is used as electrolyte, and the thickness of the electrolyte is 5mA cm -2 ～20mA cm -2 Electrodepositing, and growing copper hydroxide nanowires on the surface of the foamy copper to obtain a sample; washing the sample by using deionized water, and then placing the sample in a vacuum oven for drying to obtain a dried sample;
(2) placing the dried sample in a plasma reaction chamber at 180-250 ℃, introducing hydrogen into the plasma reaction chamber, keeping the pressure of the reaction chamber at 10-30 Pa in the glow discharge process, continuously treating for 3-10 min under the condition that the power of radio frequency plasma is 200-250W, and cooling to room temperature to obtain the copper nanowire/foam copper composite material;
2. preparation of mon@cw@cf:
(1) placing the copper nanowire/foam copper composite material in an ALD reaction cabin, vacuumizing the cabin, keeping the pressure in the reaction cabin at 0.5Torr, heating to 200-220 ℃, introducing molybdenum hexacarbonyl, ozone and water vapor into the reaction cabin according to a circularly set program for circular deposition, and enabling molybdenum oxide to grow layer by layer on the surface of the copper nanowire/foam copper composite material to obtain the molybdenum oxide/copper nanowire/foam copper composite material;
(2) placing the molybdenum oxide/copper nanowire/foam copper composite material in a plasma reaction chamber at 350-450 ℃, introducing ammonia gas into the plasma reaction chamber, keeping the pressure of the reaction chamber at 10-30 Pa in the glow discharge process, continuously treating for 2-5 min under the condition that the power of radio-frequency plasma is 200-250W, and cooling to room temperature to obtain the molybdenum nitride coated copper nanowire/foam copper current collector with a lithium-philic gradient.
Use of a molybdenum nitride coated copper nanowire/copper foam current collector with a lithium-philic gradient on a lithium metal battery anode.
The invention has the advantages that:
the invention provides a preparation method of a molybdenum nitride layer coated copper nanowire composite foam copper (MoN@CW@CF) three-dimensional anode current collector and application thereof to a lithium metal battery anode; the invention grows the copper nanowire structure on the surface of the foam copper through simple electrochemical deposition, dehydration and reduction processes; the copper nanofibers provide a large number of charge centers and electrochemical sites, and can uniformly distribute the surface charge of the foam copper frame; the Atomic Layer Deposition (ALD) and ammonia plasma nitridation are used for depositing a uniform molybdenum nitride layer on the surface of the copper nanowire, so that abundant nucleation sites are provided for lithium electroplating/stripping; because ALD only deposits one side of the substrate, the molybdenum oxide gradient distribution in the vertical direction is realized on the foam copper substrate, and the molybdenum oxide layer is rapidly nitrided into a lithium-philic molybdenum nitride layer through ammonia plasma treatment; the uniform ultrathin lithium-philic layer and the submicron nanowire layer play a vital role in inhibiting the formation of lithium dendrites and dead lithium for the current collector; meanwhile, the foam copper structure has good mechanical properties, and ensures high structural stability of the anode in the process of rapid repeated electroplating and stripping.
The invention has the advantages that:
the invention tests the electrical property of the obtained molybdenum nitride coated copper nanowire/foam copper anode material, and the result shows that the electrical property is 1mA cm -2 And a current density of 1mAh cm -2 Under the surface capacity, the average coulomb efficiency of the half battery assembled by MoN@CW@CF is up to 98% in 240 cycles, and the assembled symmetrical battery can stably circulate for 1200h, which proves that the anode material of the lithium metal battery provided by the invention has excellent lithium electroplating/stripping stability; when combined with LiFePO 4 When the cathode is matched with the anode,the Mon@CW@CF electrode showed 133.8mAh g after 250 cycles -1 The high specific discharge capacity and the high capacity retention rate of 98.6 percent indicate that the anode material of the lithium metal battery provided by the invention has higher cycle life.
Drawings
FIG. 1 is a schematic flow chart of a molybdenum nitride coated copper nanowire/copper foam current collector with a lithium-philic gradient prepared in example 1;
FIG. 2 is a photograph of sample at different experimental stages in example 1, where a is CF, b is CW@CF, c is a MoN@CW@CF surface layer, and d is a MoN@CW@CF bottom layer;
FIG. 3 is a scanning electron microscope image of a sample, wherein a and b are CF, c and d are CW@CF, and e and f are MoN@CW@CF;
FIG. 4 is an XPS spectrum, wherein a is an XPS spectrum of Mo3d and b is an XPS spectrum of N1 s;
FIG. 5 is a scanning electron microscope image of the electrode obtained after deposition of lithium in example 2, wherein a is a Li@CF electrode, b is a Li@CW@CF electrode, and c is a Li@MoN@CW@CF electrode;
FIG. 6 is a graph of a MoN@CW@CF assembled half cell prepared in example 3 using example 1 at 1mAcm -2 A coulombic efficiency plot below;
FIG. 7 is a graph of the cycling stability of the symmetrical cell assembled in example 4 using the MoN@CW@CF prepared in example 1;
fig. 8 is a graph of coulombic efficiency and discharge capacity of a li@mon@cw@cf electrode assembled using li@mon@cw@cf electrode prepared in example 2 in example 5.
Detailed Description
The first embodiment is as follows: the preparation method of the molybdenum nitride coated copper nanowire/foam copper current collector with the lithium-philic gradient is specifically completed according to the following steps:
1. preparing a copper nanowire/foam copper composite material:
(1) copper foam is used as a working electrode, a platinum sheet is used as a counter electrode, potassium hydroxide solution is used as electrolyte, and the thickness of the electrolyte is 5mA cm -2 ～20mA cm -2 Electrodepositing, and growing copper hydroxide nanowires on the surface of the foamy copper to obtain a sample; sample alignment using deionized waterCleaning the product, and then placing the product in a vacuum oven for drying to obtain a dried sample;
(2) placing the dried sample in a plasma reaction chamber at 180-250 ℃, introducing hydrogen into the plasma reaction chamber, keeping the pressure of the reaction chamber at 10-30 Pa in the glow discharge process, continuously treating for 3-10 min under the condition that the power of radio frequency plasma is 200-250W, and cooling to room temperature to obtain the copper nanowire/foam copper composite material;
2. preparation of mon@cw@cf:
(1) placing the copper nanowire/foam copper composite material in an ALD reaction cabin, vacuumizing the cabin, keeping the pressure in the reaction cabin at 0.5Torr, heating to 200-220 ℃, introducing molybdenum hexacarbonyl, ozone and water vapor into the reaction cabin according to a circularly set program for circular deposition, and enabling molybdenum oxide to grow layer by layer on the surface of the copper nanowire/foam copper composite material to obtain the molybdenum oxide/copper nanowire/foam copper composite material;
(2) placing the molybdenum oxide/copper nanowire/foam copper composite material in a plasma reaction chamber at 350-450 ℃, introducing ammonia gas into the plasma reaction chamber, keeping the pressure of the reaction chamber at 10-30 Pa in the glow discharge process, continuously treating for 2-5 min under the condition that the power of radio-frequency plasma is 200-250W, and cooling to room temperature to obtain the molybdenum nitride coated copper nanowire/foam copper current collector with a lithium-philic gradient.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the thickness of the foam copper in the step one (1) is 300 mu m-2 mm. The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the concentration of the potassium hydroxide solution in the step one (1) is 1mol/L to 2mol/L. The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the electrodeposition time in the step one (1) is 5-20 min. The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the temperature of the drying in the step one (1) is 60-100 ℃, and the drying time is 6-12 h. Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the flow rate of the hydrogen in the step (2) is 10sccm to 20sccm. Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: the number of cyclic depositions in the step two (1) is 150-300 times. Other steps are the same as those of embodiments one to six.
Eighth embodiment: one difference between the present embodiment and the first to seventh embodiments is that: the cycle setting program is as follows: (1) introducing molybdenum hexacarbonyl for 0.3s; (2) nitrogen purging for 60s; (3) introducing water vapor for 5s; (4) nitrogen purging for 5s; (5) introducing ozone for 0.03s; (6) nitrogen purging for 50s. The other steps are the same as those of embodiments one to seven.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: and (2) the flow rate of the ammonia gas in the step (2) is 10 sccm-20 sccm. Other steps are the same as those of embodiments one to eight.
Detailed description ten: the embodiment is an application of a molybdenum nitride coated copper nanowire/foam copper current collector with a lithium-philic gradient on an anode of a lithium metal battery.
The following examples are used to verify the benefits of the present invention:
example 1: the preparation method of the molybdenum nitride coated copper nanowire/foam copper current collector with the lithium-philic gradient comprises the following steps:
1. preparing a copper nanowire/foam copper composite material:
(1) copper Foam (CF) is used as a working electrode, a platinum sheet is used as a counter electrode, and potassium hydroxide with concentration of 1mol/L is used for dissolvingThe solution was used as an electrolyte at 10mA cm -2 Electrodepositing for 20min, and growing copper hydroxide nanowires on the surface of the foamy copper to obtain a sample; washing the sample by using deionized water, and then placing the sample in a vacuum oven at 60 ℃ to dry for 6 hours to obtain a dried sample;
(2) placing the dried sample in a plasma reaction chamber at 200 ℃, introducing 15sccm hydrogen into the plasma reaction chamber, keeping the pressure of the reaction chamber at 10Pa in the glow discharge process, continuously treating for 5min under the condition that the power of radio frequency plasma is 250W, and cooling to room temperature to obtain a copper nanowire/foam copper composite material (CW@CF);
2. preparation of mon@cw@cf:
(1) placing the copper nanowire/foam copper composite material in an ALD reaction cabin, vacuumizing the cabin, keeping the pressure in the reaction cabin at 0.5Torr, heating to 220 ℃, introducing molybdenum hexacarbonyl, ozone and water vapor into the reaction cabin according to a circularly set program for circular deposition, and enabling molybdenum oxide to grow layer by layer on the surface of the copper nanowire/foam copper composite material to obtain the molybdenum oxide/copper nanowire/foam copper composite material;
the number of cyclic depositions in the step two (1) is 300 cycles; the cycle setting program is as follows: (1) introducing molybdenum hexacarbonyl for 0.3s; (2) nitrogen purging for 60s; (3) introducing water vapor for 5s; (4) nitrogen purging for 5s; (5) introducing ozone for 0.03s; (6) nitrogen purging for 50s;
(2) placing the molybdenum oxide/copper nanowire/foam copper composite material in a plasma reaction chamber at 400 ℃, introducing 15sccm ammonia gas into the plasma reaction chamber, keeping the pressure of the reaction chamber at 10Pa in the glow discharge process, continuously treating for 2min under the condition that the power of radio-frequency plasma is 250W, and cooling to room temperature to obtain the molybdenum nitride coated copper nanowire/foam copper current collector (MoN@CW@CF) with a lithium-philic gradient.
In the embodiment, three-dimensional porous foam copper is used as a template, copper hydroxide nanowires are prepared by an electrochemical deposition method, the obtained nanowires are dehydrated and reduced to obtain copper nanowires, and a compact secondary structure is formed on the surface of the foam copper; and then, nitriding by ALD molybdenum oxide and ammonia plasma to obtain a uniform molybdenum nitride layer, and constructing a three-dimensional main structure with gradient in the vertical direction by taking one side with the lithium-philic molybdenum nitride layer as the bottom layer of the electrode plate, wherein the flow schematic diagram is shown in figure 1.
FIG. 2 is a photograph of sample at different experimental stages in example 1, where a is CF, b is CW@CF, c is a MoN@CW@CF surface layer, and d is a MoN@CW@CF bottom layer;
as can be seen from fig. 2: the Copper Foam (CF) was gold colored (fig. 2 a), the nanowire/copper foam composite (cw@cf) was dark red (fig. 2 b), the top layer of mon@cw@cf was copper nanowires without molybdenum oxide deposited, the color was unchanged, and still dark red (fig. 2 c). The bottom layer of mon@cw@cf is brownish black due to the presence of the molybdenum nitride layer (fig. 2 d).
FIG. 3 is a scanning electron microscope image of a sample, wherein a and b are CF, c and d are CW@CF, and e and f are MoN@CW@CF;
FIG. 3 (a, b) is a scanning electron microscope image of Copper Foam (CF) at different magnifications, and it can be seen that the surface is bare and smooth; fig. 3 (c, d) is a scanning electron microscope image of copper nanowires/copper foam (cw@cf) at different magnifications, dense nanowires are grown on the smooth surface of copper foam, and these nanowires are connected to each other to form a secondary structure of the current collector, the specific surface area of the current collector is increased, and the diameter of the copper nanowire is about 100nm. Fig. 3 (e, f) is a scanning electron microscope image of molybdenum nitride/copper nanowire/copper foam (mon@cw@cf) at different magnifications, and it can be seen that the structure is still nanowire-shaped, but the nanowire diameter increases to around 300nm, indicating the presence of a deposited layer on the surface.
FIG. 4 is an XPS spectrum, wherein a is an XPS spectrum of Mo3d and b is an XPS spectrum of N1 s;
from FIG. 4a, it can be seen that the molybdenum in the sample is Mo 3+ The successful preparation of the lithium-philic molybdenum nitride layer can be demonstrated by the invention in combination with the presence of the N-Mo bond in fig. 4 b.
Example 2: the Li@MoN@CW@CF electrode is completed by the following steps:
the button cell was assembled using mon@cw@cf prepared in example 1 as the positive electrode, copper nanowire/foam copper side close to the separator, lithium sheet as the negative electrode, and electrolysisSolution selection 1M LITFSI was dissolved in DOL/DME (v: v=1:1) +2% LiNO 3 The positive and negative electrode surfaces were 40 microliters each. At 0.25mAcm -2 For 20h at a current density of 5mAhcm on a Mon@CW@CF electrode -2 After the battery is disassembled, a Li@MoN@CW@CF electrode is obtained; the 1M LITFSI was dissolved in DOL/DME (v: v=1:1) +2% LiNO 3 Is LITFSI and LiNO 3 Dissolving the mixture into a mixed solution of DOL and DME to obtain an electrolyte, wherein the volume ratio of DOL to DME in the mixed solution of DOL and DME is 1:1, the concentration of LITFSI in the electrolyte is 1mol/L, and the concentration of LiNO in the electrolyte is 1mol/L 3 The mass fraction of (2%).
According to the same method, taking CF as a positive electrode, depositing lithium ions on the surface of the CF to obtain a Li@CF electrode;
according to the same method, taking CW@CF as an anode, depositing lithium ions on the surface of the CW@CF to obtain a Li@CW@CF electrode;
FIG. 5 is a scanning electron microscope image of the electrode obtained after deposition of lithium in example 2, wherein a is a Li@CF electrode, b is a Li@CW@CF electrode, and c is a Li@MoN@CW@CF electrode;
it can be seen from fig. 5 a and b that dendritic lithium grows largely in the pore structure of the copper foam, and the deposited lithium covers only the upper surface of the skeleton. The current collector prepared by the invention does not generate dendritic lithium, and a foam copper structure still exists, which indicates that lithium ions are deposited in the foam copper.
Example 3: the assembly of half cells using mon@cw@cf prepared in example 1 was accomplished by the following steps:
the coin cell was assembled using mon@cw@cf prepared in example 1 as the positive electrode, copper nanowires/foam copper side close to the separator, lithium sheet as the negative electrode, and electrolyte solution was 1M LITFSI dissolved in DOL/DME (v: v=1:1) +2% LiNO 3 The positive and negative electrode surfaces were 40 microliters each. At 1mA cm -2 Is 1mAh cm -2 Performing half-cell testing under the surface capacity of the battery; the 1M LITFSI was dissolved in DOL/DME (v: v=1:1) +2% LiNO 3 Is LITFSI and LiNO 3 Dissolving the mixture into a mixed solution of DOL and DME to obtain an electrolyte, wherein the volume ratio of DOL to DME in the mixed solution of DOL and DME is 1:1, and the concentration of LITFSI in the electrolyte is1mol/L，LiNO 3 The mass fraction of (2%).
FIG. 6 is a graph of MoN@CW@CF assembled half cell prepared in example 3 using example 1 at 1mA cm -2 A coulombic efficiency plot below;
FIG. 6 shows a half cell assembled using MoN@CW@CF prepared in example 1 at a current density of 1mAh cm -2 Electroplating capacity of 1mAh cm -2 In the case of (2), an average coulombic efficiency of greater than 98% can be maintained over 240 cycles. This shows that mon@cw@cf has good reversibility and high lithium utilization.
The symmetrical cells were assembled to further investigate the reversibility of the prepared electrodes.
Example 4: the symmetrical cell assembled using mon@cw@cf prepared in example 1 was completed as follows:
the coin cell was assembled using mon@cw@cf prepared in example 1 as the positive electrode, copper nanowires/foam copper side close to the separator, lithium sheet as the negative electrode, and electrolyte solution was 1M LITFSI dissolved in DOL/DME (v: v=1:1) +2% LiNO 3 The positive and negative electrode surfaces were 40 microliters each. At 0.25mA cm -2 For 20h at a current density of 5mAh cm on a Mon@CW@CF electrode -2 After 1mA cm of lithium -2 Is 1mAh cm -2 Performing a symmetrical battery test at a surface capacity of (1); the 1M LITFSI was dissolved in DOL/DME (v: v=1:1) +2% LiNO 3 Is LITFSI and LiNO 3 Dissolving the mixture into a mixed solution of DOL and DME to obtain an electrolyte, wherein the volume ratio of DOL to DME in the mixed solution of DOL and DME is 1:1, the concentration of LITFSI in the electrolyte is 1mol/L, and the concentration of LiNO in the electrolyte is 1mol/L 3 The mass fraction of (2%).
FIG. 7 is a graph of the cycling stability of the symmetrical cell assembled in example 4 using the MoN@CW@CF prepared in example 1;
FIG. 7 is a graph of current density at 1mA cm for a symmetrical cell assembled using MoN@CW@CF prepared in example 1 -2 The cycle stability measured below, the Li/MoN@CW@CF electrode can operate for more than 1200 hours, and in addition, the voltage hysteresis (VH, gap between lithium plating voltage and stripping voltage) is only 17mV, which proves that the anode current collector prepared by the invention can effectively inhibit reversible deposition of lithiumThe growth of lithium dendrites is suppressed, thereby improving the cycle stability.
Li@MoN@CW@CF is combined with commercially available LiFePO 4 (LFP) pairing, the electrochemical performance of the full cell was studied. The LFP electrode had a thickness of about 70 μm and a mass loading of active material of about 4mg cm -2 。
Example 5: the li@mon@cw@cf electrode assembly prepared using example 2 was completed as follows:
using the li@mon@cw@cf prepared in example 2 as negative electrode, copper nanowire/foam copper side close to separator, liFePO 4 (LFP) as positive electrode assembled button cell, electrolyte was 1M LIPF 6 Dissolved in EC/DEC/DMC (v: v=1:1:1) +5% FEC, 50 μl each on the positive and negative surfaces. Full cell charge and discharge testing was performed at a current density of 1C.
The 1M LIPF 6 The FEC dissolved in EC/DEC/DMC (v: v=1:1:1) +5% was LIPF 6 And dissolving the FEC into the mixed solution of the EC, the DEC and the DMC to obtain an electrolyte, wherein the volume ratio of the EC, the DEC and the DMC in the mixed solution of the EC, the DEC and the DMC is 1:1:1; LIPF in the electrolyte 6 The concentration of (2) is 1mol/L, and the mass fraction of FEC is 5%;
FIG. 8 is a graph of coulombic efficiency and discharge capacity of a full cell of Li@MoN@CW@CF|LFP assembled using the Li@MoN@CW@CF electrode prepared in example 2;
fig. 8 can be seen: li@MoN@CW@CF||LFP full cell with 135.7mAh g at 1C -1 And 98.6% high capacity retention. These results demonstrate that the lithium metal battery anode materials provided by the present invention can provide good specific discharge capacity and cycle life.
Claims (10)
1. The preparation method of the molybdenum nitride coated copper nanowire/foam copper current collector with the lithium-philic gradient is characterized by comprising the following steps of:
1. preparing a copper nanowire/foam copper composite material:
(1) copper foam is used as a working electrode, a platinum sheet is used as a counter electrode, and potassium hydroxide is dissolvedThe solution was used as an electrolyte at 5mA cm -2 ～20mA cm -2 Electrodepositing, and growing copper hydroxide nanowires on the surface of the foamy copper to obtain a sample; washing the sample by using deionized water, and then placing the sample in a vacuum oven for drying to obtain a dried sample;
(2) placing the dried sample in a plasma reaction chamber at 180-250 ℃, introducing hydrogen into the plasma reaction chamber, keeping the pressure of the reaction chamber at 10-30 Pa in the glow discharge process, continuously treating for 3-10 min under the condition that the power of radio frequency plasma is 200-250W, and cooling to room temperature to obtain the copper nanowire/foam copper composite material;
2. preparation of mon@cw@cf:
(1) placing the copper nanowire/foam copper composite material in an ALD reaction cabin, vacuumizing the cabin, keeping the pressure in the reaction cabin at 0.5Torr, heating to 200-220 ℃, introducing molybdenum hexacarbonyl, ozone and water vapor into the reaction cabin according to a circularly set program for circular deposition, and enabling molybdenum oxide to grow layer by layer on the surface of the copper nanowire/foam copper composite material to obtain the molybdenum oxide/copper nanowire/foam copper composite material;
(2) placing the obtained molybdenum oxide/copper nanowire/foam copper composite material in a plasma reaction chamber at 350-450 ℃, introducing ammonia gas into the plasma reaction chamber, keeping the pressure of the reaction chamber at 10-30 Pa in the glow discharge process, continuously treating for 2-5 min under the condition that the power of radio-frequency plasma is 200-250W, and cooling to room temperature to obtain the molybdenum nitride coated copper nanowire/foam copper current collector with a lithium-philic gradient.
2. The method for preparing a molybdenum nitride coated copper nanowire/copper foam current collector with a lithium-philic gradient according to claim 1, wherein the thickness of the copper foam in the step one (1) is 300 μm-2 mm.
3. The method for preparing the molybdenum nitride coated copper nanowire/foam copper current collector with the lithium-philic gradient according to claim 1, wherein the concentration of the potassium hydroxide solution in the step one (1) is 1 mol/L-2 mol/L.
4. The method for preparing a molybdenum nitride coated copper nanowire/copper foam current collector with a lithium-philic gradient according to claim 1, wherein the electrodeposition time in the step one (1) is 5-20 min.
5. The method for preparing the molybdenum nitride coated copper nanowire/foam copper current collector with the lithium-philic gradient according to claim 1, wherein the drying temperature in the step one (1) is 60-100 ℃, and the drying time is 6-12 h.
6. The method for preparing a molybdenum nitride coated copper nanowire/copper foam current collector with a lithium-philic gradient according to claim 1, wherein the flow rate of hydrogen in the step one (2) is 10 sccm-20 sccm.
7. The method for preparing a molybdenum nitride coated copper nanowire/copper foam current collector with a lithium-philic gradient according to claim 1, wherein the number of cyclic depositions in the step two (1) is 150-300 cycles.
8. The method for preparing the molybdenum nitride coated copper nanowire/foam copper current collector with the lithium-philic gradient according to claim 1 or 7, wherein the cyclic setting procedure is as follows: (1) introducing molybdenum hexacarbonyl for 0.3s; (2) nitrogen purging for 60s; (3) introducing water vapor for 5s; (4) nitrogen purging for 5s; (5) introducing ozone for 0.03s; (6) nitrogen purging for 50s.
9. The method for preparing the molybdenum nitride coated copper nanowire/foam copper current collector with the lithium-philic gradient according to claim 1, wherein the flow of the ammonia gas in the second step (2) is 10 sccm-20 sccm.
10. The use of a molybdenum nitride coated copper nanowire/copper foam current collector with a lithium-philic gradient prepared by the preparation method according to claim 1, wherein the use of a molybdenum nitride coated copper nanowire/copper foam current collector with a lithium-philic gradient on the anode of a lithium metal battery.
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