CN114538410A - 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 a lithium metal secondary battery are provided. 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 the mixture at the temperature of 600-plus-1100 ℃ and preserving the heat for a period of time to obtain the multi-layer carbon-coated lithium-philic element carbon microsphere. The lithium-philic core at the center of the carbon microsphere takes up lithium atoms and serves as a preferential deposition site to guide the lithium atoms to be preferentially deposited at the lithium-philic site in the carbon sphere. With the increase of the deposition capacity, lithium atoms are deposited between the carbon layers from the inner layer to the outer layer, the gradient lithium-philic structure can effectively utilize the space of a carrier, and the concentric thin-shell layered structure can well buffer the volume change caused by the deposition and stripping process of lithium metal. The preparation method is simple, and the material is used as a carrier material of the cathode of the lithium metal secondary battery, so that the growth of lithium dendrite can be effectively inhibited, the uniform and controllable deposition and stripping of lithium metal can be guided, and the long cycle stability is shown.
Description
Technical Field
The invention relates to the field of composite lithium metal negative electrodes and lithium metal secondary batteries, in particular to a modified carbon microsphere material, a preparation method and application thereof in a negative electrode carrier or a current collector of a lithium metal battery.
Background
Conventional lithium ion batteries (lithium metal free rechargeable batteries) are not satisfactory for higher energy density battery systems. The metallic lithium has low oxidation-reduction potential (-3.04V vs H) as the negative electrode+/H2) And a high theoretical capacity (3860mAh g-1) The lithium secondary battery cathode material is considered to be ideal, and not only can be matched with a traditional cathode, but also has great application potential in high-capacity non-lithium-intercalation cathode materials (such as Air, S, Sn and the like). However, lithium metal as a negative electrode also presents some very troublesome problems, the most important of which is the safety problem caused by the uncontrolled growth of dendrites, volume expansion caused by non-uniform lithium deposition leading to electrode powdering; the electrolyte is depleted by repeated breaking of the SEI caused by side reactions due to dead lithium caused by polarization. Therefore, low deposition stripping efficiency is exhibited in addition to the safety problem in long-term cyclic use.
At present, the problem is mainly solved from three aspects, namely interface engineering of electrode electrolyte contact, design of novel electrolyte and additives, and design of current collector and carrier (frame) materials of electrodes (chem.rev.2017,117, 10403-10473). The main idea for solving the problem in terms of interface engineering and electrolyte (including solid electrolyte) is to construct a mechanical physical barrier or modify a 'blocking' method for improving SEI strength and the like to inhibit the growth of lithium dendrites and not to radically change the spontaneous growth behavior of the dendrites. Recently, 107Ah Energy density 417Wh kg, which was just commercialized by SES (solid Energy systems)-1The lithium metal battery of (1) also predicts when dendrites may occur, primarily by polymer coating to protect the lithium metal, high concentration of electrolyte and additives to inhibit lithium dendrite growth and battery data detection systems (SES website www.masscec.com).
The electrode current collector side frame material is used as a carrier for lithium metal deposition, and mainly provides a specific framework structure by using the material to relieve volume and interface changes caused by metal lithium in a circulation process so as to improve the circulation stability. The method is an effective method for solving the problem from the aspect of 'dredging', and the main measure is to construct a carrier of lithium-philic elements and sites to guide lithium metal to be deposited on the carrier. Lithium-philic matrices and elements have been extensively studied and many metals, non-metals such as Au, Ag, Cu, Si, Sn, N, O, B, etc. have been widely reported to have affinity for lithium and to induce uniform deposition and exfoliation of lithium, but the large volume change during deposition exfoliation tends to cause swelling pulverization, resulting in poor long cycle performance for lithium metal deposition exfoliation (ACS Energy lett.2021,6, 4118-. The conductive framework material can provide rapid electron transport, reduce local current density, and uniformly deposit lithium. Researchers have used a number of conductive carriers to regulate lithium deposition, such as metallic copper foams, nickel foams; non-metal carbon particles, carbon fibers, carbon cloth, graphene, nano materials, etc. (Energy Storage mater.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 material with great prospect in a metal lithium carrier. The existing method generally comprises the step of carrying out lithiophilic treatment on the surface of a carrier to guide the nucleation and growth of lithium atoms on the surface of the carrier, which achieves the effect of uniform lithium metal deposition to a certain extent, but the lithium metal is also easy to deposit on the outer surface of the carrier, and the pores are blocked to reduce the integral volume specific capacity of the electrode and generate dendrites (Nano Lett.2020,20, 3681-3687).
The prior research proves that the effective effect of the lithium metal cathode carrier material on stabilizing lithium metal is still an unsolved problem of establishing efficient nucleation sites in carriers including carbon materials to guide the lithium metal to be deposited at specified positions in the carriers.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the lithium-philic onion carbon microsphere and the preparation method thereof to regulate the growth of dendritic crystals, guide lithium metal to the designated position of the carrier material for uniform deposition and construct a stable lithium metal secondary battery cathode. The lithium-philic carbon microsphere has the following morphological structure characteristics:
the appearance is a micron spherical shape, the lithium-philic elements are wrapped by amorphous carbon sheet layers in a layer-by-layer mode in a sphere center oriented arrangement, and finally the carbon sphere with a particle size of 1-10um and a similar concentric circle structure containing the lithium-philic elements is formed.
The technical scheme of the invention is as follows: a preparation method of lithium-philic onion carbon microspheres 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 and dissolving or dispersing the lithium-philic source in a liquid carbon source, and carrying out heat clearing and melting on a solid carbon source and then re-dispersing and mixing the lithium-philic source;
step (2) injecting the liquid mixture obtained in step (1) into an inert atmosphere (N) at a certain flow rate2Or Ar) protection and heated to 800-1300 ℃ for pyrolysis carbonization, and the temperature is reduced to room temperature after a period of heat preservation to obtain the lithium-philic onion carbon microspheres;
the carbon source in the step (1) comprises: one or a mixture of pyridine, pyrrole, N-methyl pyrrolidone (NMP), chitosan, asphalt, aromatic hydrocarbon heavy oil, benzene, toluene and naphthalene;
the lithium-philic source in the step (1) comprises: one or a mixture of a nano gold salt solution, a nano silver ion solution, a nano silicon ion solution, a nano tin ion solution and a nano tin ion solution;
the liquid injection mode in the step (2) comprises titration method injection and ultrasonic atomization method injection;
the carbon source of the step (1): the molar mass ratio of the lithium-philic source is 1: (0-0.5);
the lithium-philic onion carbon microsphere is applied to a negative electrode carrier material of a lithium metal secondary battery.
The invention has the following advantages:
according to the invention, the carbon source and the lithium-philic source are mixed and then directly pyrolyzed in one step, the process is simple and efficient, and the lithium-philic source is effectively dispersed into the carbon microspheres.
The carbon microsphere not only plays a role of a conductive agent and effectively disperses a lithium-philic source to prevent lithium atoms from locally gathering to grow lithium dendrites, but also limits a lithium-philic matrix into the carbon matrix, thereby preventing the lithium-philic matrix from directly contacting with an electrolyte, reducing the reaction activity of lithium-philic metal and effectively preventing pulverization. The formed gradient lithium-philic structure finally achieves the aim of directionally controlling the storage of lithium atoms from the inner layer to the designated position of the outer layer of the carbon sphere, and a lithium cage for storing lithium is formed.
Drawings
FIG. 1 shows the microscopic morphology of lithium-philic carbon microspheres by scanning electron microscopy.
FIG. 2 is a curve of capacity-voltage during the process of lithium metal deposition and stripping for lithium-philic carbon microspheres.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples, but the present invention is not limited thereto.
Example 1
Stirring pyridine and silver nitrate according to the mass ratio of 6:1 for reaction for 30-60min, sucking into an injection pump, then dripping 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.
The obtained lithium-philic carbon microsphere is shown in figure 1, the average particle size is about 1-2 μm, the specific form is that metal silver particles are wrapped by an onion-shaped carbon layer, the carbon layer rich in nitrogen is formed by pyrolysis of pyridine, so that the carbon sphere has better lithium-philic property compared with a pure carbon material, the silver wrapped inside has higher lithium-philic property, when electrons obtained on the surface of lithium ions are reduced into lithium atoms, the lithium ions are adsorbed on the surface of the carbon sphere, and then the silver particles with stronger lithium-philic property inside the carbon sphere are used as the driving force of the lithium atoms moving into the carbon layer to enable the lithium atoms to preferentially move into the carbon sphere. The nucleation overpotential of lithium metal deposition shown in fig. 2 is obviously reduced compared with that of pure copper foil, which shows that lithium atoms are easier to nucleate in the lithium-philic carbon spheres and are more beneficial to uniformly depositing lithium metal at a later stage, and the gradient lithium-philic structure can effectively utilize the space of a carrier, and simultaneously the thin-shell layered structure can well buffer the volume change brought in the process of depositing and stripping lithium metal, so that the lithium-philic gradient structure has long-term cycling stability.
Example 2
Stirring pyridine and silver nitrate according to the mass ratio of 6:1 for reaction for 30-60min, sucking into an injection pump, then dripping 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 microspheres with smaller particle size, and the agglomeration of the carbon microspheres is more obvious after the heat preservation time is prolonged. The test result of the efficiency of taking the lithium-philic carbon ball with certain temperature and pyrolysis time for electrochemical deposition and lithium metal stripping shows that the lithium-philic carbon ball can keep about 99 percent of stable deposition and stripping circulation more than 400 circles.
Example 3
Mixing pyridine and nano silicon powder according to a certain mass ratio, performing ultrasonic dispersion stirring for a certain time to enable the two phases to be uniform, 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 the heat for 10min after the injection pyrolysis is finished, and cooling to obtain the lithium-philic carbon microspheres.
Example 4
Mixing N-methylpyrrolidone and silver nitrate according to a mass ratio of 10:1, stirring for 30-60min to enable two phases to be uniform, sucking the two phases into an injection pump, then dripping the mixture into a shaft furnace protected by argon atmosphere at 900 ℃ 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.
One kind of lithium-philic carbon microsphere is used for battery short circuit test, and the result shows that the lithium-philic carbon microsphere guides lithium to be uniformly deposited, so that the short circuit time exceeds 300 hours.
Example 5
Uniformly mixing medium-temperature asphalt (with a softening point of 50-90 ℃) powder and nano silicon powder according to a mass ratio of 8:1, heating to 120 ℃ with stirring, continuously stirring for 30-60min, injecting into an injection pump with pre-heat preservation of 120 ℃, then dropping 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.
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 pre-heat preservation of 100 ℃, then dripping into a vertical furnace protected by argon atmosphere at 1300 ℃ according to a certain flow rate, preserving heat for 30min after injection pyrolysis is finished, and cooling to obtain the lithium-philic carbon microspheres.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. A lithium-philic onion carbon microsphere, a preparation method and application of a lithium metal secondary battery thereof are characterized in that:
the appearance is a micron spherical shape, and the lithium-philic elements are wrapped layer by the amorphous carbon sheet layer along the orientation arrangement of the sphere center, and finally the carbon sphere with the similar concentric circular structure and the particle size of 1-10um and containing the lithium-philic elements is formed.
2. The lithium-philic onion carbon microsphere, the preparation method and the application of the lithium metal secondary battery thereof as claimed in claim 1, wherein the lithium-philic onion carbon microsphere comprises the following components in percentage by weight: 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 in a liquid carbon source, and carrying out heat clearing and melting on a solid carbon source and then re-dispersing and mixing the lithium-philic source; step (2) injecting the liquid mixture obtained in step (1) into an inert atmosphere (N) at a certain flow rate2Or Ar) protection and is heated to 800-1300 ℃ for pyrolysis carbonization, and the temperature is reduced to room temperature after a period of heat preservation to obtain the lithium-philic onion carbon microspheres.
3. The lithium-philic onion carbon microsphere, the preparation method and the lithium metal secondary battery application of the lithium-philic onion carbon microsphere as claimed in claims 1 and 2, wherein the carbon source comprises: pyridine, pyrrole, N-methyl pyrrolidone (NMP), chitosan, asphalt, aromatic heavy oil, benzene, toluene, naphthalene or their mixture.
4. The li-philic onion carbon microsphere, the preparation method and the lithium metal secondary battery application of the same as in claims 1 and 2, wherein the li-philic source comprises: one or a mixture of nano gold and a salt solution thereof, a solution of nano silver and ions thereof, a solution of nano silicon and ions thereof, and a solution of nano tin and ions thereof.
5. The method for preparing lithium-philic carbon microspheres as claimed in claim 2, wherein: the molar mass ratio of the carbon source to the lithium-philic source in the step (1) is 1: (0-0.5).
6. A lithium-philic carbon microsphere obtained by the method of claims 1 to 5 for use in lithium metal secondary batteries, including liquid electrolyte lithium metal secondary batteries and (quasi-) solid electrolyte lithium metal secondary batteries.
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| WO2024000102A1 (en) * | 2022-06-27 | 2024-01-04 | 宁德时代新能源科技股份有限公司 | Negative electrode sheet and preparation method therefor, secondary battery, battery module, battery pack, and electric device |
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| WO2024000102A1 (en) * | 2022-06-27 | 2024-01-04 | 宁德时代新能源科技股份有限公司 | Negative electrode sheet and preparation method therefor, secondary battery, battery module, battery pack, and electric device |
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