CN114538410B - Lithium-philic onion carbon microsphere, preparation method and application of lithium metal secondary battery - Google Patents
Lithium-philic onion carbon microsphere, preparation method and application of lithium metal secondary battery Download PDFInfo
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Abstract
A preparation method of lithium-philic onion carbon microspheres and application of the lithium-philic onion carbon microspheres in lithium metal secondary batteries. Uniformly mixing a carbon source and a lithium-philic source according to a certain proportion, then injecting the mixture into a vertical furnace protected by inert gas, carbonizing at 600-1100 ℃ and preserving heat for a period of time to obtain the carbon microsphere with the multi-layer carbon coating of the lithium-philic element. The lithium-philic nucleus in the center of the carbon microsphere absorbs lithium atoms and serves as a preferential deposition site, and the lithium atoms are led to be preferentially deposited at the lithium-philic site in the carbon microsphere. Along with the increase of the deposition capacity, lithium atoms are deposited between the carbon layers from the inner layer to the outer layer, and the gradient lithium-philic structure can effectively utilize the carrier space, and the concentric thin-shell layered structure can well buffer the volume change caused by the lithium metal deposition stripping process. The preparation process is simple, and the material is used as a carrier material of the negative electrode of the lithium metal secondary battery, can effectively inhibit growth of lithium dendrite and guide uniform and controllable deposition stripping of lithium metal, and shows long cycle stability.
Description
Technical Field
The application relates to the field of composite lithium metal cathodes and lithium metal secondary batteries, in particular to a modified carbon microsphere material, a preparation method and application thereof in a lithium metal battery cathode carrier or current collector.
Background
Conventional lithium ion batteries (non-lithium metal rechargeable batteries) are not satisfactory for higher energy density battery system applications. Metallic lithium as a negative electrode has a low oxidation-reduction potential (-3.04V vs H) + /H 2 ) And a high theoretical capacity (3860 mAh g -1 ) Is considered as an ideal negative electrode material for lithium secondary batteries, which can be matched with a traditional positive electrode and has high capacity of non-lithium intercalation positive electrode materials (such as Air, S, sn and the like)Large application potential. However, metallic lithium also presents some very tricky problems as a negative electrode, among which is foremost the safety problem caused by the uncontrolled dendrite growth, the volume expansion caused by the non-uniform lithium deposition leading to electrode pulverization; dead lithium caused by polarization and repeated rupture of the electrolyte due to side reactions are depleted. Therefore, it exhibits low deposition peeling efficiency in addition to safety problems in long-term recycling.
At present, the problems are mainly solved from three aspects, namely interface engineering of electrode electrolyte contact, design of novel electrolyte and additives, and design of carrier (framework) materials of current collectors and electrodes (chem. Rev.2017,117, 10403-10473). The main idea of interface engineering and electrolyte (including solid electrolyte) solution to this problem is to construct a mechanical physical barrier or modify to improve "blocking" methods such as SEI strength to inhibit lithium dendrite growth without radically changing the spontaneous growth behavior of dendrites. Recently, 107Ah energy density 417Wh kg, which was recently commercialized by SES (Solid Energy Systems) company in the early stage -1 Also, the lithium metal battery of (2) is mainly prepared by polymer coating to protect lithium metal, high concentration electrolyte and additives to inhibit the growth of lithium dendrites and battery data detection system to predict the possible occurrence time of dendrites (SES website www.masscec.com).
The electrode current collector side frame material is used as a carrier for lithium metal deposition, and a specific framework structure is provided by using the material to relieve the volume and interface change caused by metal lithium in the circulation process so as to improve the circulation stability. This is an effective way to solve this problem from the "dredging" point of view, the main measure being to build up a support of lithium-philic elements and sites to guide the deposition of lithium metal onto the support. The lithium-philic matrix and elements have been widely studied and many metals, non-metals such as Au, ag, cu, si, sn, N, O, B, etc. have been widely reported to find their affinity for lithium and to guide uniform deposition and exfoliation of lithium, but the vast volume changes during deposition exfoliation tend to cause swelling pulverization, resulting in poor long-cycle performance of lithium metal deposition exfoliation (ACS Energy lett.2021,6, 4118-4126). The conductive backbone material can provide rapid electron transport, reduce local current density, and thereby uniformly deposit lithium. Researchers have used many conductive carriers to regulate the deposition of lithium, such as metallic copper foam, nickel foam; nonmetallic carbon particles, carbon fibers, carbon cloth, graphene, nanomaterials, and the like (Energy Storage material 2021,41, 448-465). The carbon material has the advantages of high conductivity, low cost, stability and the like, so that the carbon material becomes a very promising material in a metal lithium carrier. The existing method is to conduct the lithiation treatment on the surface of the carrier to lead the nucleation growth of lithium atoms on the surface of the carrier, which achieves the effect of uniform lithium metal deposition to a certain extent, but lithium metal is also easy to deposit on the outer surface of the carrier, so that the pores are blocked to reduce the volume specific capacity of the whole electrode and dendrite is generated (Nano Lett.2020,20, 3681-3687).
The prior studies demonstrate the effective role of lithium metal anode support materials in stabilizing lithium metal, creating efficient nucleation sites in the support, including carbon materials, to guide deposition of lithium metal to specified locations in the support remains an unresolved problem.
Disclosure of Invention
Aiming at the defects of the prior art, the application aims to provide a lithium-philic onion carbon microsphere and a preparation method thereof for regulating and controlling dendrite growth, guiding lithium metal to be uniformly deposited at a designated position of a carrier material, and constructing a stable lithium metal secondary battery cathode. The lithium-philic carbon microsphere has the following morphological structural characteristics:
the appearance is in a micron spherical shape, the amorphous carbon sheet layers are arranged layer by layer along the spherical center orientation, and finally the carbon sphere with the similar concentric circle structure containing the lithium-philic elements and the particle size of 1-10um is formed.
The technical scheme of the application is as follows: a preparation method of a lithium-philic onion carbon microsphere comprises the following specific steps:
uniformly mixing or dissolving a carbon source and a lithium-philic source according to a certain mass ratio, directly stirring, mixing, dissolving or dispersing the lithium-philic source for a liquid carbon source, and re-mixing and mixing the lithium-philic source after the solid carbon source is subjected to fever melting;
step (2) the liquid mixture of step (1) is injected into an inert atmosphere (N) at a certain flow rate 2 Or Ar) are protected and addedCarrying out pyrolysis carbonization in a vertical furnace heated to 800-1300 ℃, and cooling to room temperature after heat preservation for a period of time to obtain lithium-philic onion carbon microspheres;
the carbon source of step (1) comprises: one or a mixture of pyridine, pyrrole, N-methyl pyrrolidone (NMP), chitosan, asphalt, aromatic heavy oil, benzene, toluene and naphthalene;
the lithium-philic source of step (1) comprises: one or a mixture of nano gold and a salt solution thereof, nano silver and an ion solution thereof, nano silicon and an ion solution thereof, and nano tin and an ion solution thereof;
the liquid injection mode in the step (2) comprises titration injection and ultrasonic atomization injection;
the carbon source of step (1): the molar mass ratio of the lithium philic source is 1: (0-0.5);
the lithium-philic onion carbon microsphere is prepared by the method and is applied to a negative electrode carrier material of a lithium metal secondary battery.
The application has the following advantages:
according to the application, the carbon source and the lithium-philic source are mixed and then subjected to one-step direct pyrolysis, and the process is simple and efficient, so that the lithium-philic source is effectively dispersed into the carbon microsphere.
The carbon microsphere provided by the application not only plays a role in conducting agent and effectively dispersing a lithium-philic source and preventing lithium atoms from locally aggregating and growing lithium dendrites, but also has the function of limiting the lithium-philic matrix into the carbon matrix, so that the direct contact between the lithium-philic matrix and electrolyte is avoided, the reactivity of lithium-philic metal is reduced, and pulverization is effectively prevented. The formed gradient lithium-philic structure finally achieves the aim of directionally controlling the storage of lithium atoms from the inner layer to the outer layer of the carbon sphere to form a lithium cage for storing lithium.
Drawings
FIG. 1 shows the microscopic morphology of a scanning electron microscope of the lithium-philic carbon microsphere.
FIG. 2 is a graph of capacity versus voltage during the exfoliation of lithium metal deposition from a lithium-philic carbon microsphere.
Detailed Description
The present application will be described in detail below with reference to the drawings and examples, but is not limited thereto.
Example 1
And (3) stirring pyridine and silver nitrate according to a mass ratio of 6:1, reacting for 30-60min, sucking the mixture into an injection pump, dripping the mixture into a vertical furnace protected by argon atmosphere at 1000 ℃ according to a certain flow rate, preserving heat for 30min after injection pyrolysis is finished, and cooling to obtain the lithium-philic carbon microspheres.
As shown in figure 1, the average particle size of the obtained lithium-philic carbon microsphere is about 1-2 μm, the metal silver particles are wrapped by onion-shaped carbon layers, pyridine is pyrolyzed to form a carbon layer rich in nitrogen elements, so that the carbon microsphere has better lithium-philic property compared with a pure carbon material, silver wrapped inside has higher lithium-philic property, when lithium ions are reduced to lithium atoms on the surface of the lithium ions, the lithium ions are adsorbed on the surface of the carbon microsphere, and then the silver particles with stronger lithium-philic property inside the carbon microsphere are used as driving force for the lithium atoms to move into the carbon layer, so that the lithium atoms move into the carbon microsphere preferentially. The nucleation overpotential of lithium metal deposition is obviously reduced compared with that of pure copper foil as shown in fig. 2, which shows that lithium atoms are easier to nucleate in the lithium-philic carbon sphere and are more favorable for uniformly depositing lithium metal in the later period, and the gradient lithium-philic structure can effectively utilize the carrier space and simultaneously buffer the volume change brought by the process of depositing and stripping lithium metal by the lamellar structure of the thin shell, so that the lithium-philic carbon sphere has long-term circulation stability.
Example 2
And (3) stirring pyridine and silver nitrate according to a mass ratio of 6:1, reacting for 30-60min, sucking the mixture into an injection pump, dripping the mixture into a vertical furnace protected by argon atmosphere at 1100 ℃ according to a certain flow rate, preserving heat for 10-30min after injection pyrolysis is finished, and cooling to obtain the lithium-philic carbon microspheres.
The pyrolysis temperature is increased to obtain the lithium-philic carbon microsphere with smaller particle size, and the agglomeration of the carbon microsphere is more obvious when the heat preservation time is prolonged. The test result of electrochemical deposition stripping lithium metal by taking the lithium-philic carbon sphere with a certain temperature and pyrolysis time shows that the lithium-philic carbon sphere can keep about 99% stable deposition stripping cycle over 400 circles.
Example 3
Mixing pyridine and nano silicon powder according to a certain mass ratio, performing ultrasonic dispersion and stirring for a certain time to uniformly obtain two phases, then sucking the two phases into an injection pump, then dripping the two phases into a vertical furnace protected by argon atmosphere at 1100 ℃ according to a certain flow rate, preserving heat for 10min after injection pyrolysis is finished, and cooling to obtain the lithium-philic carbon microspheres.
Example 4
Mixing N-methyl pyrrolidone and silver nitrate according to the mass ratio of 10:1, stirring for 30-60min to ensure that two phases are uniform, then sucking the mixture into an injection pump, then dripping the mixture into a vertical furnace protected by argon atmosphere at 900 ℃ according to a certain flow rate, preserving heat for 30min after injection pyrolysis is finished, and cooling to obtain the lithium-philic carbon microspheres.
One of the lithium-philic carbon microspheres is taken for battery short-circuit test, and the result shows that the lithium-philic carbon microsphere guides lithium to be deposited uniformly so that the short-circuit time exceeds 300 hours.
Example 5
Uniformly mixing medium-temperature asphalt (softening point 50-90 ℃) powder and nano silicon powder according to the mass ratio of 8:1, heating to 120 ℃ with stirring, continuously stirring for 30-60min, injecting into a pre-heat preserving injection pump at 120 ℃, then dripping into a 1000 ℃ vertical furnace protected by argon atmosphere according to a certain flow rate, preserving heat for 30min after injection pyrolysis is finished, and cooling to obtain the lithium-philic carbon microspheres.
Example 6
Uniformly mixing naphthalene powder and nano silicon powder according to the mass ratio of 10:1, heating to 100 ℃ with stirring, continuously stirring for 30-60min, injecting into an injection pump with the temperature of 100 ℃ being kept pre-heat, then dripping into a vertical furnace with the argon atmosphere of 1300 ℃ according to a certain flow rate, keeping the temperature for 30min after injection pyrolysis is finished, and cooling to obtain the lithium-philic carbon microspheres.
While the preferred embodiment of the present application has been described in detail, the present application is not limited to the embodiment, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the present application, and these equivalent modifications and substitutions are intended to be included in the scope of the present application as defined in the appended claims.
Claims (5)
1. A lithium-philic onion carbon microsphere, characterized in that:
the appearance is in a micron spherical shape, the amorphous carbon sheet layers are arranged in a direction along the sphere center to wrap the lithium-philic elements layer by layer, and finally the concentric circle-like structure carbon sphere containing the lithium-philic elements with the particle size of 1-10 mu m is formed.
2. The method for preparing the lithium-philic onion carbon microsphere as claimed in claim 1, wherein the method comprises the following steps:
the preparation method comprises the following steps:
uniformly mixing or dissolving a carbon source and a lithium-philic source according to a certain mass ratio, directly stirring, mixing and dissolving or dispersing the lithium-philic source for a liquid carbon source, and re-mixing and mixing the lithium-philic source after the solid carbon source is subjected to heat relieving and melting; step (2) injecting the liquid mixture of step (1) into N at a certain flow rate 2 Or Ar protected and heated to 800-1300 ℃ in a vertical furnace for pyrolysis carbonization, and cooling to room temperature after heat preservation for a period of time to obtain the lithium-philic onion carbon microsphere; the molar mass ratio of the carbon source to the lithium-philic source in the step (1) is 1: x is more than 0 and less than or equal to 0.5.
3. The method for preparing the lithium-philic onion carbon microsphere as claimed in claim 2, wherein the method comprises the following steps:
the carbon source includes: pyridine, pyrrole, N-methylpyrrolidone (NMP), chitosan, asphalt, aromatic heavy oil, benzene, toluene, naphthalene or a mixture thereof.
4. The method for preparing the lithium-philic onion carbon microsphere as claimed in claim 2, wherein the method comprises the following steps:
the lithium-philic source includes: the nano gold and the salt solution thereof, the nano silver and the ion solution thereof, the nano silicon and the ion solution thereof, the nano tin and the ion solution thereof or the mixture thereof.
5. Use of the lithium-philic onion carbon microsphere of claim 1 and the lithium-philic onion carbon microsphere obtained by the method of claims 2-4 in lithium metal secondary batteries, including liquid electrolyte lithium metal secondary batteries and solid electrolyte lithium metal secondary batteries.
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