CN109950547B - Three-dimensional current collector decorated with non-noble metal coating - Google Patents
Three-dimensional current collector decorated with non-noble metal coating Download PDFInfo
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- CN109950547B CN109950547B CN201910239910.8A CN201910239910A CN109950547B CN 109950547 B CN109950547 B CN 109950547B CN 201910239910 A CN201910239910 A CN 201910239910A CN 109950547 B CN109950547 B CN 109950547B
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Abstract
The invention discloses a three-dimensional current collector modified with a non-noble metal coating, wherein the non-noble metal coating is nanoparticles of any one of nickel, iron, zinc, magnesium, aluminum, tin and copper, and the diameter of the nanoparticles is 1-1000 nm. The invention also discloses a preparation method of the three-dimensional current collector and a metal secondary battery cathode prepared by the three-dimensional current collector. The three-dimensional current collector provided by the invention has the advantages of easily available raw materials, low cost, easiness in operation, suitability for large-scale production and the like, has high lithium affinity, accelerates the penetration rate of molten lithium, reduces nucleation overpotential, realizes uniform deposition of metal, inhibits dendritic crystal growth, and has better constant-current charge and discharge performance.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a three-dimensional current collector modified with a non-noble metal coating, a preparation method of the three-dimensional current collector and a metal secondary battery cathode prepared from the three-dimensional current collector.
Background
With the continuous development of energy storage devices such as portable electronic devices, electric vehicles, smart grid storage and the like, secondary batteries directly using metal cathodes such as lithium, sodium, potassium, magnesium and the like have been widely used due to their high energy density. Take a lithium metal secondary battery as an example because of its high theoretical specific capacity (3860mA hr g)-1) Low reduction potential (-3.04V relative to standard hydrogen electrode) and light weight, and assembled secondary battery, such as Li-O2The energy density of the battery and the Li-S battery is several times that of the current commercial lithium ion battery, and the lithium ion battery has important scientific and application values.
The metal negative electrode has many problems at present, firstly, metal ions are deposited unevenly in the deposition-precipitation process to form dendritic crystals, which easily causes short circuit in the battery and brings serious potential safety hazards. Secondly, the metal has high activity and is easy to react with the organic liquid electrolyte to form an unstable Solid Electrolyte Interface (SEI), resulting in low deposition-precipitation efficiency. Third, the metal undergoes large volume expansion and contraction during the deposition-precipitation process. Therefore, development of a safe and efficient metal negative electrode is urgently required.
In order to solve the problems associated with the metal negative electrode, researchers have performed many works, such as optimizing electrolyte composition, designing an interface protection layer, developing a solid electrolyte, and constructing a new three-dimensional current collector. The three-dimensional current collector is adopted, so that the specific surface area of the electrode can be increased, the local current density is reduced, the growth of dendrites is inhibited, and the huge volume change of the electrode is relieved. However, the commonly used three-dimensional current collector has lithium-phobic characteristics and shows a large nucleation overpotential, so that it is difficult to combine metallic lithium into the three-dimensional current collector by an industrialized melting injection method. At present, the lithium affinity of the surface interface is usually controlled by noble metals such as gold and silver, and alloy layers such as lithium-silicon alloy and lithium-indium alloy. However, these materials are expensive or unstable to air, and are difficult to industrialize. Therefore, the method for finding the surface regulation and control means which is low in cost, simple and easy to scale improves the lithium affinity characteristic of the three-dimensional current collector interface, constructs a composite metal negative electrode, inhibits the formation of dendritic crystals in the battery and the change of the electrode volume, and has important significance for constructing a metal secondary battery with high safety and high energy density.
Disclosure of Invention
The invention aims to provide a three-dimensional current collector modified with a non-noble metal coating, a preparation method of the three-dimensional current collector and a metal secondary battery cathode prepared from the three-dimensional current collector.
The above purpose is realized by the following technical scheme:
the three-dimensional current collector modified with the non-noble metal coating is a nanoparticle of any one of nickel, iron, zinc, magnesium, aluminum, tin and copper, and the diameter of the nanoparticle is 1-1000 nm. Further preferably, the diameter of the nanoparticles is 50-500 nm.
Preferably, the three-dimensional current collector is a carbon fiber.
A method for preparing the non-noble metal coating modified three-dimensional current collector, comprising the following steps:
(1) cutting the three-dimensional current collector carbon fiber, placing the cut three-dimensional current collector carbon fiber into strong acid, stirring the three-dimensional current collector carbon fiber in water bath at the temperature of 60-150 ℃ for 2-20h, taking the three-dimensional current collector carbon fiber out, cleaning the carbon fiber with ultrapure water, and drying the carbon fiber.
(2) Putting the carbon fiber into a nickel nitrate solution with the concentration of 0.01-2mol/L, preserving the heat for 1-10h at the temperature of 40-100 ℃, taking out and drying.
(3) And then, calcining the carbon fiber at high temperature in an inert gas atmosphere to graphitize the carbon fiber, cooling to room temperature, and then placing in reducing gas for annealing to reduce nickel ions into nano nickel and load the nano nickel on the surface of the carbon fiber.
Preferably, the strong acid is concentrated sulfuric acid and concentrated nitric acid, and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1.
preferably, the concentration of the nickel nitrate solution is 0.025 mol/L.
Preferably, the high-temperature calcination temperature is 1200-1400 ℃, the temperature-rising speed is 2-20 ℃/min, and the calcination time is 20-120 min.
Preferably, the annealing temperature is 700-900 ℃, the temperature rising speed is 2-20 ℃/min, and the annealing time is 60-180 min.
The metal secondary battery cathode is prepared by melting metal lithium, sodium, potassium and magnesium and then loading the melted metal lithium, sodium, potassium and magnesium on the three-dimensional current collector modified with the non-noble metal coating.
Compared with the prior art, the invention has the following advantages:
1) the lithium-philic coating modified by the three-dimensional current collector provided by the invention is non-noble metal such as nickel, iron, zinc, magnesium, aluminum, tin, copper and the like, and compared with the method adopting noble metal such as gold, silver and alloy, the lithium-philic coating modified by the three-dimensional current collector provided by the invention has the advantages of easily obtained raw materials, low cost, easiness in operation, suitability for large-scale production and the like, and has very high practicability.
2) According to the invention, the nano lithium-philic coating is modified, so that the prepared three-dimensional current collector has high lithium-philic property, the penetration rate of the three-dimensional current collector to molten lithium is accelerated, and the preparation of the lithium battery cathode can be completed within 5 minutes.
3) The invention can realize the uniform deposition of the metal lithium, inhibit the growth of dendrites and stabilize the electrode structure, so that the negative electrode of the metal secondary battery has better constant-current charge-discharge performance, can stabilize overpotential, improve the cycling stability of the battery, reduce voltage polarization and improve the reversible capacity and cycle times of the electrode.
Drawings
Fig. 1 is the overpotential test result of the symmetrical battery assembled in example 1.
Fig. 2 is the results of the cycle stability test of the symmetrical battery assembled in example 1.
Fig. 3 is a long cycle performance test result of the secondary battery assembled in example 1.
Fig. 4 is the overpotential test result of the symmetrical battery assembled in example 2.
Fig. 5 is the cycle stability test results for the symmetrical battery assembled in example 2.
Fig. 6 is the overpotential test result of the symmetrical battery assembled in example 3.
Fig. 7 is the cycle stability test results for the symmetrical battery assembled in example 3.
Fig. 8 is the overpotential test result of the symmetrical cell assembled in comparative example 1.
Fig. 9 is the result of the cycle stability test of the symmetrical battery assembled in comparative example 1.
Fig. 10 is the overpotential test result of the symmetrical cell assembled in comparative example 2.
Fig. 11 is the result of the cycle stability test of the symmetrical battery assembled in comparative example 2.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
Preparing a current collector modified with a non-noble metal lithium-philic coating
(1) Cutting commercial three-dimensional current collector carbon fibers, placing the cut commercial three-dimensional current collector carbon fibers in strong acid consisting of concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1), stirring for 6 hours under the condition of 80 ℃ water bath, taking out the commercial three-dimensional current collector carbon fibers, cleaning the commercial three-dimensional current collector carbon fibers with ultrapure water, and drying. The surface of the treated carbon fiber becomes smooth and has a structure which is staggered transversely and longitudinally by observing through a scanning electron microscope.
(2) And (3) putting the carbon fiber after acid treatment into a nickel nitrate solution with the concentration of 0.025mol/L, preserving the heat for 3h at the temperature of 80 ℃, taking out and drying to enable nickel nitrate to be adsorbed on the surface of the carbon fiber.
(3) Then, the carbon fiber is calcined at high temperature in the argon atmosphere, the temperature is raised to 1300 ℃ at the speed of 5 ℃/min and is kept for 1H, the carbon fiber is graphitized, the carbon fiber is placed in reducing gas (H) after being cooled to the room temperature2: ar is 5:95) is annealed, the temperature is raised to 800 ℃ at the speed of 5 ℃/min and is kept for 2h, so that nickel ions are reduced into nano nickel and loaded on the surface of the carbon fiber. It can be seen from the scanning electron microscope that the nickel particles are uniformly distributed on the surface of the carbon fiber, and the particles have a uniform size and an average particle diameter of about 100 nm.
(II) preparing the cathode of the metal secondary battery
And (2) punching the nickel-loaded carbon fiber into a wafer with the diameter of 10mm, heating the wafer together with the metal lithium to melt the metal lithium into liquid, injecting the liquid into a pore structure of the carbon fiber, taking the carbon fiber out of the molten metal lithium, and cooling the carbon fiber to room temperature to obtain the cathode of the lithium secondary battery. It can be seen that the surface of the carbon fiber is completely covered with metallic lithium and exhibits a metallic luster. Because the surface of the carbon fiber is covered with nickel particles, the lithium affinity of the carbon fiber is increased, the penetration rate of the carbon fiber to molten lithium is accelerated, and the whole process takes about 5 minutes. The cross-sectional thickness of the carbon fiber after lithium melting is about 300 μm, which is similar to the cross-sectional thickness of the carbon fiber before lithium melting.
(III) Assembly of symmetrical batteries and Performance testing thereof
The lithium-supporting carbon fibers were used as a positive electrode and a negative electrode, respectively, as a Celgard separator, containing 1% of LiNO3The lithium | Li symmetric battery was assembled from the LiTFSI electrolyte of the mixed solvent (1: 1 (volume ratio) of DOL and DME. The battery is subjected to constant-current charge and discharge test by using a blue test system, and the test cut-off capacity is 1mA h cm-2The test temperature was 25 ℃. FIG. 1 is the Li | LiSymmetric cell at 0.5mA cm-2The overpotential of the first loop under the current density is tested, and the overpotential of the cathode is relatively stable and is about 28 mV; FIG. 2 shows the Li | Li symmetric cell at 0.5mA cm-2The cycling stability under the current density can be seen that the voltage still keeps stable after 2000 hours of cycling, and the voltage polarization is very small and finally stabilizes at about 10 mV.
(IV) electrochemical testing of lithium Metal Secondary batteries
The prepared lithium-loaded carbon fiber negative electrode, positive electrode material (lithium iron phosphate positive electrode LFP) and Celgard diaphragm contain 1 percent of LiNO3And assembling the solution of DOL and DME in a volume ratio of 1:1 (in terms of volume ratio) with a LiTFSI electrolyte to obtain the lithium metal secondary battery. The surface capacity of the lithium iron phosphate anode is higher than 3mA h cm-2The test cut-off voltage is 2-4V, the test temperature is 25 ℃, and the test current density is 0.2-1.0C. FIG. 3 shows that the reversible capacity of the CF/Ni @ Li | LFP electrode can approach 160mA h g-2And the capacity retention rate is 95.6 percent after 100 cycles.
Example 2
The other conditions were the same as in example 1 except that the concentration of the nickel nitrate solution in step (II) was 0.1 mol/L. After the concentration of the nickel nitrate solution is increased, the loading amount of nickel particles on the surface of the carbon fiber is obviously increased, and the size of the nickel particles is slightly increased and is about 200 nm. The number of nickel particles on the surface of the carbon fiber is increased, so that the lithium affinity of the carbon fiber is enhanced, the lithium melting rate is further accelerated, and the whole process takes about 4 minutes. After the carbon fiber is loaded with lithium, a symmetrical battery is assembled to test the electrochemical performance of the battery, and figure 4 shows that the lithium negative electrode is 0.5mA cm-2From the test result of the first-turn overpotential under the current density, it can be seen that the overpotential of the negative electrode slightly fluctuates and is between 30 and 40mV, and fig. 5 shows that the performance test of the symmetrical battery assembled by the lithium-loaded carbon fiber has poor cycle performance, and the polarization begins to increase after 1250 hours and is about 40 mV.
Example 3
The other conditions were the same as in example 1 except that the concentration of the nickel nitrate solution in step (II) was 0.2 mol/L. With increasing concentration of nickel nitrate solution, nickel particles on carbon fiber surfaceThe loading was further increased and the size of the nickel particles was significantly increased, about 500 nm. The lithium affinity of the carbon fiber is further enhanced due to the increase of nickel particles on the surface of the carbon fiber, the lithium melting rate is accelerated, and the whole process takes about 3 minutes. After the carbon fiber is loaded with lithium, a symmetrical battery is assembled to test the electrochemical performance of the battery, and FIG. 6 shows that the lithium cathode is at 0.5mA cm-2The first ring of overpotential test under current density shows that the overpotential fluctuation of the negative electrode is large and is about 40mV, and fig. 7 shows that the cycle performance is further reduced in the performance test of the symmetrical battery assembled by the lithium-loaded carbon fiber, and the polarization begins to increase after 1000h and tends to 50 mV.
Example 4
The other conditions were the same as in example 1 except that the acid-treated carbon fiber was placed in a ferric nitrate solution having a concentration of 0.025 mol/L. The lithium affinity of the surface of the carbon fiber loaded with the iron nano particles is obviously increased, and the lithium melting rate in the whole process is about 3.5 minutes. The assembled symmetrical cell was at 0.5mA cm-2The first turn of overpotential under current density is about 45 mV.
Example 5
The other conditions were the same as in example 1 except that the acid-treated carbon fiber was placed in a zinc nitrate solution having a concentration of 0.025 mol/L. The lithium affinity of the surface of the carbon fiber loaded with the zinc nanoparticles is obviously increased, and the lithium melting rate in the whole process is about 2 minutes. The assembled symmetrical cell was at 0.5mA cm-2The first turn of the overpotential at current density is around 25 mV.
Example 6
The other conditions were the same as in example 1 except that the acid-treated carbon fiber was placed in a tin nitrate solution having a concentration of 0.025 mol/L. The lithium affinity of the surface of the carbon fiber loaded with the tin nano-particles is obviously increased, and the lithium melting rate in the whole process is about 3 minutes. The assembled symmetrical cell was at 0.5mA cm-2The first turn of the overpotential at the current density is about 35 mV.
Comparative example 1
The difference from example 1 is that the carbon fibers are subjected to the step (one) onlyAcid treatment, no other subsequent modification. The surface of the pure carbon cloth is relatively smooth and is characterized by transverse and longitudinal staggering. Because the pure carbon fiber has no obvious lithium affinity, the whole lithium melting process can only absorb liquid lithium by virtue of a pore structure, and is slow and can be finished in 10 minutes. After melting lithium, cooling to room temperature, and assembling into a symmetrical battery, FIG. 8 shows the lithium negative electrode at 0.5mA cm-2The overpotential of the negative electrode reaches 30mV by the first-turn overpotential test under the current density, and as can be seen from FIG. 9, the cycle performance of the symmetrical battery assembled after melting lithium by pure carbon cloth is poor, and the polarization starts to increase obviously after 1000h, and finally is about 50 mV.
Comparative example 2
The difference from the embodiment 1 is that the carbon fiber after acid treatment is replaced by the foam nickel, and the carbon fiber is cleaned and dried without other subsequent modification. The surface of the foamed nickel is relatively smooth and has a three-dimensional porous structure. Because the nickel foam has a bulk phase structure, the whole lithium melting process can be completed within about 12 minutes, the lithium is melted and then cooled to room temperature, and then the lithium negative electrode is assembled into a symmetrical battery, and fig. 10 shows that the lithium negative electrode is 0.5mA cm/cm-2The overpotential of the negative electrode exceeds 100mV by the first-turn overpotential test under the current density, and the cycle performance of the symmetrical battery assembled after the foamed nickel melts the lithium is very poor, the voltage is extremely unstable, and the fluctuation is large as can be seen from FIG. 11.
Comparative example 3
The difference from the example 1 is that the acid-treated carbon fiber is replaced by nickel foil, washed, dried and not subjected to other subsequent modification. The nickel foil surface was characterized to be relatively smooth and free of significant porosity. Because the lithium affinity of the nickel foil is poor, the whole lithium melting process can be finished within about 13 minutes, the molten lithium can be assembled into a symmetrical battery to test the cycle performance and the voltage polarization of the battery, the overpotential of the negative electrode reaches 110mV, and the overpotential is obviously increased compared with other examples and comparative examples.
Claims (1)
1. A preparation method of a metal secondary battery cathode is characterized by comprising the following steps: the metal secondary battery negative electrode is prepared by melting metal lithium and then loading the molten metal lithium on a three-dimensional current collector modified with a non-noble metal coating, and the preparation method of the three-dimensional current collector modified with the non-noble metal coating comprises the following steps: (1) cutting the three-dimensional current collector carbon fiber, and placing the cut three-dimensional current collector carbon fiber in a volume ratio of 3:1, stirring the mixture in concentrated sulfuric acid and concentrated nitric acid at the temperature of 80 ℃ for 6 hours in a water bath, taking out the mixture, cleaning the carbon fibers with ultrapure water, and drying the carbon fibers;
(2) putting the carbon fiber after acid treatment into a nickel nitrate solution with the concentration of 0.025mol/L, preserving heat for 3 hours at the temperature of 80 ℃, taking out and drying to enable nickel nitrate to be adsorbed on the surface of the carbon fiber;
(3) and then, calcining the carbon fiber with the nickel nitrate adsorbed on the surface at high temperature in an inert gas atmosphere, heating to 1300 ℃ at the speed of 5 ℃/min, preserving the heat for 1h to graphitize the carbon fiber, cooling to room temperature, then placing in a reducing gas to anneal, heating to 800 ℃ at the speed of 5 ℃/min, preserving the heat for 2h to reduce nickel ions into nano nickel, and loading the nano nickel on the surface of the carbon fiber.
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| CN111403704A (en) * | 2020-03-19 | 2020-07-10 | 江苏师范大学 | Preparation method and application of three-dimensional dendritic metal-carbon nanofiber |
| CN111710851B (en) * | 2020-04-27 | 2022-04-01 | 常州赛得能源科技有限公司 | Solid-state battery and preparation method thereof |
| CN111668493A (en) * | 2020-06-16 | 2020-09-15 | 南开大学 | Three-dimensional current collector for inhibiting dendritic crystal of lithium metal negative electrode and application of three-dimensional current collector in metal lithium battery |
| CN112382764B (en) * | 2020-11-12 | 2022-03-01 | 武汉理工大学 | Lithium-philic copper-nickel double-metal-layer modified three-dimensional framework material and preparation method and application thereof |
| CN112490425B (en) * | 2020-11-23 | 2023-01-03 | 南方科技大学 | Flexible composite lithium metal electrode, preparation thereof and lithium metal battery |
| CN112909234A (en) * | 2021-01-20 | 2021-06-04 | 合肥工业大学 | Preparation method and application of lithium cathode or sodium cathode |
| CN113346134A (en) * | 2021-05-27 | 2021-09-03 | 华中科技大学 | Precursor solution for preparing polymer electrolyte and application thereof |
| CN117174914A (en) * | 2023-09-20 | 2023-12-05 | 中能鑫储(北京)科技有限公司 | Three-dimensional current collector applied to aluminum ion battery and preparation method thereof |
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