CN114400302B - Porous carbon microsphere and preparation method thereof, carbon-lithium composite material, negative electrode and lithium metal battery - Google Patents
Porous carbon microsphere and preparation method thereof, carbon-lithium composite material, negative electrode and lithium metal battery Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention discloses a porous carbon microsphere, a preparation method thereof, a carbon-lithium composite material, a negative electrode and a lithium metal battery, wherein the porous carbon microsphere has a three-dimensional open pore structure, and the porous carbon microsphere comprises a conductive agent, a lithium-philic substance and a catalyst. In the porous carbon microsphere, the three-dimensional open pore structure provides space for deposition of the metal lithium, reduces the volume effect caused by the deposition of the metal lithium, plays a role of effectively bearing huge volume expansion, reduces the contact interface between the metal lithium and electrolyte, and inhibits side reaction; the lithium-philic substances are uniformly distributed in the porous carbon microspheres, and the lithium-philic substances and the conductive agent can regulate the deposition behavior of lithium, guide the uniform deposition of metal lithium and facilitate the deposition of lithium ions inside the pore structure, thereby relieving/inhibiting the growth of lithium dendrites.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a porous carbon microsphere, a preparation method thereof, a carbon-lithium composite material, a negative electrode and a lithium metal battery.
Background
With the increasing prominence of energy and environmental problems, clean energy and renewable energy are being studied more and more, and lithium metal batteries and ion batteries are widely used in various fields such as electric automobiles, mobile electronic equipment, aerospace and the like.
However, the lithium ion battery and the lithium metal battery commercialized today still have some disadvantages, for example, the commercial lithium ion battery faces the following drawbacks: in general, the lithium ion battery takes lamellar graphite as a negative electrode, but the theoretical capacity of a graphite carbon material is very low (372 mAh g -1 ) The energy requirements in the aspects of energy storage, power and the like can not be met. As another example, lithium metal batteries suffer from the following drawbacks: firstly, lithium dendrite is formed by non-uniform deposition of lithium metal, secondly, SEI films generated by the reaction of lithium metal and electrolyte are extremely easy to break, and finally, the volume expansion of lithium metal tends to be infinite. Therefore, lithium metal is directly used as the negative electrode of the lithium ion batteryThe safety problems such as short circuit, fire explosion and the like are extremely easy to cause.
The prior art has proposed improvements such as CN107834073a to inhibit the growth of lithium dendrites by using negative dendrite inhibitors, which include polyamine additives with electron withdrawing groups and solvents; the total volume ratio of the polyamine additive solution with the electron withdrawing group is 0.05-0.2%; the solvent is lithium metal battery electrolyte, and 1M LiPF is adopted 6 Propylene carbonate solution of (a). CN104009237A is prepared by modifying graphite to obtain high-capacity negative electrode material, wherein the spherical graphite has potato-shaped or sphere-like microstructure, potato-shaped particles are uniformly scattered with graphite single-layer fragments on the surface, a hard carbon shell is wrapped outside, graphite single-layer fragments or multi-layer fragments are scattered among the particles, the average particle size of the particles is 3-50 mu m, and the specific surface area is 2.0-186m 2 Per gram, tap density of 0.2-1.5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The crystal layer interval d002 is between 0.3354 and 0.3390 nm; the potato-shaped or spherical particles of spherical graphite contain micropores with the size of 5nm-5 μm inside, and the spherical graphite is natural graphite. The obtained product has higher specific capacity and cycle stability than common products.
However, the above technology still has problems of lithium dendrite problems caused by non-uniform deposition of lithium metal, low specific capacity, and SEI film rupture caused by volume expansion.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a porous carbon microsphere and a preparation method and application thereof. According to the invention, by designing a good three-dimensional conductive structure, the deposition of lithium metal can be optimized, the lithium metal is guided to be deposited in the three-dimensional framework and the holes, the formation of lithium dendrites is reduced, the volume expansion is weakened, and meanwhile, the specific capacity is improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a porous carbon microsphere having a three-dimensional open pore structure, the porous carbon microsphere including a conductive agent, a lithium-philic substance, and a catalyst therein.
In the porous carbon microsphere of the invention, pores are interconnected to form a three-dimensional open pore structure, and the conductive agent, the lithium-philic substance and the catalyst are dispersed in the porous carbon microsphere. The technical principle is as follows: the first and the third open pore structures provide space for depositing the metal lithium, reduce the volume effect caused by the deposition of the metal lithium, play a role of effectively bearing huge volume expansion, reduce the contact interface between the metal lithium and the electrolyte and inhibit side reaction; secondly, the wettability of the carbon material and lithium metal is poor, so that the material performance is not ideal, the wettability between the carbon material and the lithium metal can be improved by introducing the conductive agent, and the lithium metal deposition is guided; the lithium-philic substances are uniformly distributed in the porous carbon microspheres, and can optimize lithium deposition sites and attract lithium metal to be uniformly deposited.
The following preferred technical solutions are used as the present invention, but not as limitations on the technical solutions provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solutions.
Preferably, the conductive agent includes at least one of conductive carbon black (SP), acetylene Black (AB), and Ketjen Black (KB).
Preferably, the raw material of the lithium-philic substance is a lithium-philic additive.
In the present invention, the lithium-philic substance may be the same as or different from the kind of the lithium-philic additive, for example, zinc oxide and Ag are the lithium-philic substances themselves.
Preferably, the lithium-philic additive includes at least one of a Zn-containing material, a Ti-containing material, a Si-containing material, and an Ag-containing material.
Preferably, the Zn-containing material comprises zinc oxide and a soluble zinc salt.
Preferably, the Ti-containing material comprises tetrabutyl titanate and TiO 2 At least one of them.
Preferably, the Si-containing material includes Si andSiO x at least one of (1), wherein 0<x<2。
Preferably, the Ag-containing material includes at least one of Ag and silver nitrate.
Preferably, the catalyst comprises a soluble nickel salt, preferably nickel chloride.
In a second aspect, the present invention provides a method for preparing the porous carbon microsphere according to the first aspect, the method comprising the steps of:
(1) Mixing a carbon source, a carbon source additive, a conductive agent, a lithium-philic additive, a catalyst and a solvent to obtain slurry;
(2) And (3) performing spray drying on the slurry obtained in the step (1), and then performing annealing carbonization treatment on a spray dried product to obtain the porous carbon microsphere.
According to the method, slurry containing raw materials such as a carbon source, a carbon source additive, a conductive agent, a lithium-philic additive and a catalyst is subjected to composite pelleting by spray drying, the catalyst has the effect of modifying the morphology of the material, the carbon source additive has the bonding effect and can bond other substances in the slurry, the carbon source and the carbon source additive are converted into carbon materials in the annealing carbonization treatment process, the catalyst changes the microscopic morphology of particles to form a three-dimensional open pore structure, and the obtained lithium-philic substances are uniformly distributed in the porous carbon microspheres, so that the porous carbon microspheres with adjustable lithium ion deposition behaviors are prepared.
The preparation method is simple and is easy for industrial expansion production.
As a preferred embodiment of the method according to the invention, the carbon source in step (1) comprises a resin, preferably a phenolic resin. The phenolic resin can generate a small amount of carbon nanotubes under the catalysis of the catalyst, and the phenolic resin has high carbon residue rate, thereby being beneficial to improving the material performance.
Preferably, the carbon source additive of step (1) is selected from at least one of polyvinylpyrrolidone, sucrose, glucose, sodium carboxymethylcellulose (CMC), styrene Butadiene Rubber (SBR) and polyethylene glycol.
Preferably, the conductive agent of step (1) includes at least one of conductive carbon black, acetylene black and ketjen black. The above preferred types of conductive agents act as nucleation cores that help promote agglomeration of the material into a porous, spherical structure.
Preferably, the lithium-philic additive of step (1) includes at least one of a Zn-containing material, a Ti-containing material, a Si-containing material, and an Ag-containing material.
Preferably, the catalyst of step (1) comprises nickel chloride.
Preferably, the raw material for preparing the slurry in the step (1) further comprises a pore-forming agent.
Preferably, the pore-forming agent in step (1) includes at least one of NaCl, KCl, urea and ammonium bicarbonate, but is not limited to the above listed types, and pore-forming agents commonly used in the art are also suitable for the present invention.
According to the preferred technical scheme, the interconnected porous structure (namely the formation of the three-dimensional open pore structure) is facilitated by introducing the pore-forming agent, so that the effect of the porous carbon microsphere on relieving volume expansion is improved.
Preferably, the solvent in step (1) comprises at least one of an alcohol and water, preferably a mixed solvent of an alcohol and water, the mass ratio of the alcohol to water being (2-4): 1, such as 2:1, 2.3:1, 2.5:1, 3:1 or 4:1, etc.
Preferably, in step (1), the mass ratio of the carbon source, the carbon source additive, the conductive agent, the lithium-philic additive, the catalyst and the pore-forming agent is 1 (0.1-0.3): (0.1-1.5): (0.01-0.05): (0-0.5), for example, 1:0.1:0.2:0.05:0.02:0.2, 1:0.1:0.5:0.05:0.02:0.5, 1:0.1:0.2:0.1:0.2, 1:0.1:0.2:0.05, 1:0.1:0.2:0.02:0.2, 1:0.1:0.2:0.1:0.2, 1:0.3:0.1:0.2, 1:0.1:0.2, and the like, (1:0.1:0.0.3:0.2) is 1:0.0.2, and the like, (1:0.1-0.0.3:0.0.2).
Preferably, the slurry of step (1) has a solids content of 1% -40%, for example 1%, 3%, 6%, 10%, 15%, 20%, 22.5%, 25%, 27%, 30%, 35% or 40% etc.
Preferably, the mixing in step (1) is performed in the following manner: adding the conductive agent into the solvent for dispersion, then adding the carbon source, the carbon source additive, the optional pore-forming agent, the lithium-philic additive and the catalyst, and stirring for dissolution. By mixing in the above preferred manner, better dispersibility can be obtained.
Preferably, the annealing carbonization treatment of step (2) is performed under a protective atmosphere, and the gas in the protective atmosphere includes at least one of nitrogen, helium, neon, argon, krypton, and xenon.
Preferably, the temperature of the annealing carbonization treatment in step (2) is 600 ℃ to 1200 ℃, for example 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 900 ℃, 950 ℃, 1000 ℃, 1100 ℃, 1200 ℃ or the like.
Preferably, the incubation time of the annealing carbonization treatment of step (2) is 1h-10h, such as 1h, 2h, 3h, 3.5h, 4h, 5h, 6h, 8h or 10h, etc.
As a further preferred embodiment of the method according to the invention, the method comprises the following steps:
(1) Adding a conductive agent into a solvent for dispersion, then adding a carbon source, a carbon source additive, an optional pore-forming agent, a lithium-philic additive and a catalyst, and stirring for dissolution to obtain slurry with the solid content of 1% -40%;
(2) Spray drying the slurry obtained in the step (1), and performing annealing carbonization treatment to obtain porous carbon microspheres;
wherein the mass ratio of the carbon source to the carbon source additive to the conductive agent to the lithium-philic additive to the catalyst to the pore-forming agent is 1 (0.1-0.3) (0.1-1.5) (0.01-0.05) (0-0.5), preferably 1 (0.1-0.3) (0.1-1.0) (0.01-0.05) (0.1-0.5). The method of the present invention may be carried out by washing, drying, etc. after the annealing carbonization treatment, and the present invention is not particularly limited.
In a third aspect, the present invention provides a carbon lithium composite material comprising the porous carbon microsphere of the first aspect, and lithium metal in the three-dimensional open pore structure of the porous carbon microsphere.
The lithium may be incorporated into the porous carbon material by, for example, electrochemical or melt compounding.
The electrochemical compounding method specifically comprises the steps of mixing a porous carbon material, a binder and a conductive agent to prepare slurry, coating the slurry on a current collector, drying the slurry to prepare a porous carbon pole piece, taking metal lithium as a counter electrode, and controlling the content of lithium metal introduced into the porous carbon by controlling current and time.
The melting compounding method specifically comprises the steps of heating porous carbon and metal lithium to a temperature above the melting point of lithium, and stirring to obtain the carbon-lithium composite material.
The invention utilizes the porous carbon microsphere of the first aspect, and lithium metal reaches 3860mAh g -1 The cathode material with better electrochemical performance is prepared by combining metallic lithium with a porous carbon material, so that the electrochemical stability of the composite material is improved, the specific capacity of the composite material is far higher than that of graphite, the overall mass energy density of the battery is improved, and meanwhile, the deposition problem of the lithium metallic cathode and the lithium dendrite problem are optimized.
Preferably, the lithium metal is present in an amount of 10% -70%, such as 10%, 20%, 30%, 40%, 50%, 60% or 70%, etc., based on 100% of the total mass of the carbon-lithium composite material.
In a fourth aspect, the present invention provides a negative electrode comprising the porous carbon microsphere of the first aspect and/or the carbon lithium composite of the third aspect.
The preparation method of the negative electrode is not limited, and the porous carbon material and the carbon lithium composite material can be respectively used as negative electrode active substances to prepare the negative electrode, can be mixed to prepare the negative electrode as the negative electrode active substances, and can be matched with other negative electrode active substances disclosed in the prior art to prepare the negative electrode.
In a fifth aspect, the present invention provides a lithium metal battery comprising the negative electrode of the fourth aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention designs an excellent three-dimensional structure material, in particular to a porous carbon microsphere, wherein pores are interconnected to form a three-dimensional open pore structure, and a conductive agent, a lithium-philic substance and a catalyst are dispersed in the porous carbon microsphere. The three-dimensional open pore structure provides space for depositing the metal lithium, reduces the volume effect caused by depositing the metal lithium, and plays a role in effectively bearing huge volume expansion; meanwhile, the contact interface between the lithium metal and the electrolyte is reduced, and the occurrence of side reaction is inhibited; the wettability between the carbon material and the lithium metal can be improved by introducing the conductive agent, the deposition of the lithium metal is guided, the lithium-philic substance is uniformly distributed in the porous carbon microsphere, lithium deposition sites can be optimized by the lithium-philic substance, the uniform deposition of the lithium metal is attracted, and the uniform deposition of the lithium metal is induced by the lithium-philic substance and the conductive agent during charge and discharge, so that the growth of lithium dendrites is relieved/inhibited, and the problems faced by the current lithium metal battery are hopefully solved.
(2) The porous carbon microsphere and the lithium metal with the lithium metal content of 3860mAh g are utilized -1 The cathode material with better electrochemical performance is prepared by combining metallic lithium with a porous carbon material, so that the electrochemical stability of the composite material is improved, the specific capacity of the composite material is far higher than that of graphite, the overall mass energy density of the battery is improved, and meanwhile, the deposition problem of the lithium metallic cathode and the lithium dendrite problem are optimized.
(3) The porous carbon microsphere can be used for preparing a carbon lithium negative electrode material by a physical and electrochemical method, can regulate and control the deposition behavior of metal lithium in the electrochemical process, provides an internal space for metal lithium deposition, and improves the electrochemical performance of a lithium-containing negative electrode.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments.
Example 1
The embodiment provides a porous carbon microsphere and a preparation method thereof, wherein the preparation method of the porous carbon microsphere comprises the following steps:
1g SP was added to an ethanol solution to disperse, followed by 10g phenolic resin, 2g C 4 H 6 O 4 Zn·2H 2 O, 1g PVP and 0.1g NiCl 2 ·6H 2 O is dissolved in the ethanol solution in turn, and the solid content of the mixed solution is 5%. Then spray drying the dispersed mixed solution by using spray drying equipment, wherein the air inlet temperature is 160 DEG CThe inlet pressure was 0.2MPa and the feed rate was 700ml/h, yielding black precursor powder. And (3) collecting black precursor powder, carrying out high-temperature annealing treatment on the precursor powder in a tube furnace by using nitrogen atmosphere, wherein the calcining temperature is 700 ℃, the heat preservation time is 3 hours, and cooling the carbon material to room temperature to obtain the carbon material.
Example 2
The embodiment provides a porous carbon microsphere and a preparation method thereof, wherein the preparation method of the porous carbon microsphere comprises the following steps:
10g SP is added into ethanol solution to disperse, and then 10g phenolic resin and 5g C are added 4 H 6 O 4 Zn.2H2O, 2gPVP and 0.5gNiCl 2 ·6H 2 O is dissolved in the ethanol solution in turn, and the solid content of the mixed solution is 5%. And then spray drying the dispersed mixed solution by using spray drying equipment, wherein the air inlet temperature is 120 ℃, the air inlet pressure is 0.4MPa, and the feeding speed is 500ml/h, so as to obtain black precursor powder. And (3) collecting black precursor powder, carrying out high-temperature annealing treatment on the precursor powder in a tube furnace by using nitrogen atmosphere, wherein the calcining temperature is 750 ℃, the heat preservation time is 3 hours, and obtaining the carbon material after the temperature is cooled to room temperature.
Example 3
The embodiment provides a porous carbon microsphere and a preparation method thereof, wherein the preparation method of the porous carbon microsphere comprises the following steps:
5g of SP is added into a mixed solution of ethanol and deionized water (the mass ratio of the ethanol to the deionized water is 7:3) for dispersion, and then 10g of phenolic resin, 1g of ZnO, 2g of PEG and 0.2g of NiCl are added 2 ·6H 2 O and 2g of NaCl were sequentially dissolved in the above mixed solution, and the solid content of the above mixed solution was 5%. And then spray drying the dispersed mixed solution by using spray drying equipment, wherein the air inlet temperature is 140 ℃, the air inlet pressure is 0.3MPa, and the feeding speed is 500ml/h, so as to obtain black precursor powder. And (3) collecting black precursor powder, carrying out high-temperature annealing treatment on the precursor powder in a tube furnace by using nitrogen atmosphere, wherein the calcining temperature is 800 ℃, the heat preservation time is 1h, and cooling the precursor powder to room temperature to obtain the carbon material containing inorganic salt. Use of deionization of inorganic salt-containing carbon materialsWashing with water for 3 times, and then drying in a blast oven at 80 ℃, wherein the dried material is the final carbon material.
Example 4
The difference from example 3 is that no pore-forming agent NaCl was added.
Example 5
The embodiment provides a porous carbon microsphere and a preparation method thereof, wherein the preparation method of the porous carbon microsphere comprises the following steps:
3g of AB was added to a mixed solution of ethanol and deionized water (mass ratio of ethanol to deionized water: 7:3) and dispersed, followed by 10g of phenolic resin, 1.5g of ZnO, 2g of sucrose and 0.1g of NiCl 2 ·6H 2 O was dissolved in the above mixed solution in order, and the solid content of the above mixed solution was 20%. And then spray drying the dispersed mixed solution by using spray drying equipment, wherein the air inlet temperature is 200 ℃, the air inlet pressure is 0.3MPa, and the feeding speed is 500ml/h, so as to obtain black precursor powder. And (3) collecting black precursor powder, carrying out high-temperature annealing treatment on the precursor powder in a tube furnace by using nitrogen atmosphere, wherein the calcining temperature is 1200 ℃, the heat preservation time is 1h, and cooling the precursor powder to room temperature to obtain the carbon material.
Example 6
The embodiment provides a porous carbon microsphere and a preparation method thereof, wherein the preparation method of the porous carbon microsphere comprises the following steps:
adding 6g KB into a mixed solution of ethanol and deionized water (the mass ratio of the ethanol to the deionized water is 3:1) for dispersing, and then adding 10g phenolic resin and 4g TiO 2 3g glucose and 0.1g NiCl 2 ·6H 2 O was dissolved in the above mixed solution in order, and the solid content of the above mixed solution was 30%. And then spray drying the dispersed mixed solution by using spray drying equipment, wherein the air inlet temperature is 180 ℃, the air inlet pressure is 0.4MPa, and the feeding speed is 600ml/h, so as to obtain black precursor powder. And (3) collecting black precursor powder, carrying out high-temperature annealing treatment on the precursor powder in a tube furnace by using nitrogen atmosphere, wherein the calcining temperature is 1100 ℃, the heat preservation time is 1.5h, and obtaining the carbon material after the temperature is cooled to room temperature.
Example 7
The embodiment provides a porous carbon microsphere and a preparation method thereof, wherein the preparation method of the porous carbon microsphere comprises the following steps:
1g SP was first dispersed in a mixed solution of ethanol and deionized water (ethanol to deionized water mass ratio of 2.5:1), followed by 10g phenolic resin, 3g Ag, 1g CMC and 0.1g NiCl 2 ·6H 2 O is dissolved in the above mixed solution in turn, and the solid content of the above mixed solution is 15%. And then spray drying the dispersed mixed solution by using spray drying equipment, wherein the air inlet temperature is 175 ℃, the air inlet pressure is 0.3MPa, and the feeding speed is 400ml/h, so as to obtain black precursor powder. And (3) collecting black precursor powder, carrying out high-temperature annealing treatment on the precursor powder in a tube furnace by using nitrogen atmosphere, wherein the calcining temperature is 1000 ℃, the heat preservation time is 2 hours, and cooling the carbon material to room temperature to obtain the carbon material.
Example 8
The embodiment provides a porous carbon microsphere and a preparation method thereof, wherein the preparation method of the porous carbon microsphere comprises the following steps:
8g of SP was first dispersed in a mixed solution of ethanol and deionized water (mass ratio of ethanol to deionized water: 3:1), followed by 10g of phenolic resin, 2.5g of nano-silica (particle size D50: 30 nm), 1.5g of SBR and 0.1g of NiCl 2 ·6H 2 O is dissolved in the above mixed solution in turn, and the solid content of the above mixed solution is 25%. And then spray drying the dispersed mixed solution by using spray drying equipment, wherein the air inlet temperature is 170 ℃, the air inlet pressure is 0.2MPa, and the feeding speed is 500ml/h, so as to obtain black precursor powder. And (3) collecting black precursor powder, carrying out high-temperature annealing treatment on the precursor powder in a tube furnace by using nitrogen atmosphere, wherein the calcining temperature is 700 ℃, the heat preservation time is 3 hours, and cooling the carbon material to room temperature to obtain the carbon material.
Example 9
The embodiment provides a porous carbon microsphere and a preparation method thereof, wherein the preparation method of the porous carbon microsphere comprises the following steps:
adding 4g of SP into a mixed solution of ethanol and deionized water (the mass ratio of the ethanol to the deionized water is 3:1) for dispersing, and then taking 10g of phenolic resin and 3.5g of nitro-resinSilver acid, 1g polyvinylpyrrolidone and 0.1g NiCl 2 ·6H 2 O was dissolved in the above mixed solution in order, and the solid content of the above mixed solution was 27%. And then spray drying the dispersed mixed solution by using spray drying equipment, wherein the air inlet temperature is 185 ℃, the air inlet pressure is 0.3MPa, and the feeding speed is 550ml/h, so as to obtain black precursor powder. And (3) collecting black precursor powder, carrying out high-temperature annealing treatment on the precursor powder in a tube furnace by using nitrogen atmosphere, wherein the calcining temperature is 900 ℃, the heat preservation time is 5 hours, and cooling the carbon material to room temperature to obtain the carbon material.
Example 10
The difference from example 3 is that the amount of ZnO added was 0.1g.
Example 11
The difference from example 3 is that the amount of ZnO added was 10g.
Example 12
The difference from example 3 is that the amount of SP added was 1g.
Example 13
The difference from example 3 is that the amount of SP added was 15g.
Comparative example 1
The difference from example 3 is that no catalyst NiCl was added 2 ·6H 2 O。
Comparative example 2
The difference from example 3 is that the lithium philic additive ZnO was not added.
Comparative example 3
The difference from example 3 is that the phenolic resin, 2gC 4 H 6 O 4 Zn·2H 2 O, 1g PVP and 0.1g NiCl 2 ·6H 2 O is directly dry-mixed and then subjected to a high-temperature annealing treatment step.
Comparative example 4
The difference from example 3 is that the carbon source additive PEG was not added.
Comparative example 5
The difference from example 3 is that the conductive agent SP is not added.
And (3) detection:
the lithium carbon negative electrode materials prepared in examples 1 to 13 and comparative examples 1 to 5 above were tested for porosity.
The lithium carbon negative electrode materials prepared in examples 1 to 13 and comparative examples 1 to 5 were fabricated into electrode sheets, respectively, and were assembled into button cells as working electrodes, with a charge cut-off voltage of 0.8V, discharge for a constant time of 10 hours, and a surface capacity of 4mAh/cm 2 The first coulombic efficiency, 50-week cycle retention, and expansion were tested and the results are shown in tables 1 and 2.
TABLE 1 first coulombic efficiency and cycle retention
TABLE 2 porosity and Pole piece expansion Rate
Analysis:
as can be seen from a comparison of example 3 with example 4, the addition of the pore-forming agent increases the porosity of the material and reduces the expansion rate of the lithium metal as deposited.
As can be seen from a comparison of example 3 with example 10 and comparative example 2, the addition of the appropriate amount of the lithium-philic substance and the pore-forming agent can enhance the porosity of the material, and the porosity of example 3 is higher than that of example 10 and comparative example 2. Further, when the addition amount of the lithium philic substance is too small or not, the effect of attracting the deposition of lithium metal is weak, and the expansion ratio at the time of the deposition of lithium metal becomes larger than that of example 3.
As is clear from the comparison of example 3 and example 11, an excessive addition amount of the lithium-philic substance decreases the porosity of the material, and the expansion ratio at the time of deposition of lithium metal becomes larger than that of example 3.
As can be seen from comparison of example 3 with example 12 and comparative example 5, the addition of an appropriate amount of the conductive agent can improve the porosity and first coulombic efficiency of the material, and the porosity and first coulombic efficiency of example 3 are higher than those of example 12 and comparative example 5.
As can be seen from comparison of example 3 with example 13, an excessive amount of the conductive agent is detrimental to the increase in porosity of the material and has a negative effect on the first coulombic efficiency of the material.
From a comparison of example 3 with comparative example 1, it is evident that the presence of the catalyst increases the first coulombic efficiency and porosity of the material and reduces the expansion.
As can be seen from comparison of example 3 and comparative example 3, the spray drying preparation method can significantly improve the porosity of the material and the electrochemical performance of the material.
As can be seen from the comparison of the embodiment 3 and the comparative example 4, the carbon source additive can stabilize the morphology of the material, improve the porosity, reduce the expansion rate of the pole piece and improve the electrochemical performance of the material.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (36)
1. A porous carbon microsphere, which is characterized in that the porous carbon microsphere has a three-dimensional open pore structure, and comprises a conductive agent, a lithium-philic substance and a catalyst;
the porous carbon microsphere is prepared by a preparation method which comprises the following steps:
(1) Mixing a carbon source, a carbon source additive, a conductive agent, a lithium-philic additive, a catalyst and a solvent to obtain slurry;
(2) And (3) performing spray drying on the slurry obtained in the step (1), and then performing annealing carbonization treatment on a spray dried product to obtain the porous carbon microsphere.
2. The porous carbon microsphere of claim 1, wherein the conductive agent comprises conductive carbon black SP.
3. The porous carbon microsphere of claim 2, wherein the conductive agent comprises acetylene black AB and/or ketjen black KB.
4. The porous carbon microsphere of claim 1, wherein the raw material of the lithium-philic substance is a lithium-philic additive.
5. The porous carbon microsphere of claim 4, wherein the lithium-philic additive comprises at least one of a Zn-containing material, a Ti-containing material, a Si-containing material, and an Ag-containing material.
6. The porous carbon microsphere of claim 5, wherein the Zn-containing material comprises ZnO and a soluble zinc salt.
7. The porous carbon microsphere of claim 5, wherein the Ti-containing material comprises tetrabutyl titanate and TiO 2 At least one of them.
8. The porous carbon microsphere of claim 5, wherein the Si-containing material comprises Si and SiO x At least one of (1), wherein 0<x<2。
9. The porous carbon microsphere of claim 5, wherein the Ag-containing material comprises at least one of Ag and silver nitrate.
10. The porous carbon microsphere of claim 1, wherein the catalyst comprises a soluble nickel salt.
11. The porous carbon microsphere of claim 10, wherein the catalyst is nickel chloride.
12. A method of preparing the porous carbon microsphere of any one of claims 1-11, comprising the steps of:
(1) Mixing a carbon source, a carbon source additive, a conductive agent, a lithium-philic additive, a catalyst and a solvent to obtain slurry;
(2) And (3) performing spray drying on the slurry obtained in the step (1), and then performing annealing carbonization treatment on a spray dried product to obtain the porous carbon microsphere.
13. The method of claim 12, wherein the carbon source of step (1) comprises a resin.
14. The method of claim 13, wherein the carbon source in step (1) is a phenolic resin.
15. The method according to claim 12, wherein the carbon source additive in the step (1) is at least one selected from polyvinylpyrrolidone, sucrose, glucose, sodium carboxymethylcellulose CMC, styrene butadiene rubber SBR, and polyethylene glycol.
16. The method of claim 12, wherein the conductive agent of step (1) comprises conductive carbon black.
17. The method of claim 16, wherein the conductive agent of step (1) comprises acetylene black and/or ketjen black.
18. The method of claim 12, wherein the lithium-philic additive of step (1) comprises at least one of a Zn-containing material, a Ti-containing material, a Si-containing material, and an Ag-containing material.
19. The method of claim 12, wherein the catalyst of step (1) comprises nickel chloride.
20. The method of claim 12, wherein step (1) further comprises a pore-forming agent in the feedstock from which the slurry is prepared.
21. The method of claim 20, wherein the pore-forming agent of step (1) comprises at least one of NaCl, KCl, urea, and ammonium bicarbonate.
22. The method of claim 12, wherein the solvent of step (1) comprises at least one of an alcohol and water.
23. The process according to claim 22, wherein the solvent in the step (1) is a mixed solvent of alcohol and water, and the mass ratio of the alcohol to the water is (2-4): 1.
24. The method according to claim 12, wherein in the step (1), the mass ratio of the carbon source, the carbon source additive, the conductive agent, the lithium-philic additive, the catalyst and the pore-forming agent is 1 (0.1-0.3): (0.1-1.5): (0.01-1): (0.01-0.05): (0-0.5).
25. The method according to claim 24, wherein in the step (1), the mass ratio of the carbon source, the carbon source additive, the conductive agent, the lithium-philic additive, the catalyst and the pore-forming agent is 1 (0.1-0.3): (0.1-1.0): (0.1-0.5): (0.01-0.05): (0.1-0.5).
26. The method of claim 12, wherein the slurry of step (1) has a solids content of 1% to 40%.
27. The method of claim 12, wherein the mixing in step (1) is performed by: adding the conductive agent into the solvent for dispersion, then adding the carbon source, the carbon source additive, the lithium-philic additive and the catalyst, and stirring for dissolution.
28. The method of claim 20, wherein the mixing in step (1) is performed by: adding the conductive agent into the solvent for dispersion, then adding the carbon source, the carbon source additive, the pore-forming agent, the lithium-philic additive and the catalyst, and stirring for dissolution.
29. The method of claim 12, wherein the annealing and carbonizing treatment in step (2) is performed in a protective atmosphere, and the gas in the protective atmosphere includes at least one of nitrogen, helium, neon, argon, krypton, and xenon.
30. The method of claim 12, wherein the annealing and carbonizing treatment in step (2) is performed at a temperature of 600 ℃ to 1200 ℃.
31. The method according to claim 12, wherein the annealing and carbonizing treatment in step (2) is carried out for a holding time of 1h to 10h.
32. The method according to claim 20, characterized in that it comprises the steps of:
(1) Adding a conductive agent into a solvent for dispersion, then adding a carbon source, a carbon source additive, a pore-forming agent, a lithium-philic additive and a catalyst, and stirring for dissolution to obtain slurry with the solid content of 1-40%;
(2) Spray drying the slurry obtained in the step (1), and performing annealing carbonization treatment to obtain porous carbon microspheres;
wherein the mass ratio of the carbon source to the carbon source additive to the conductive agent to the lithium-philic additive to the catalyst to the pore-forming agent is 1 (0.1-0.3) (0.1-1.0) (0.1-0.5) (0.01-0.05) (0.1-0.5).
33. A carbon lithium composite comprising the porous carbon microsphere of any one of claims 1-11, and lithium metal in the three-dimensional open pore structure of the porous carbon microsphere.
34. The carbon-lithium composite material according to claim 33, wherein the content of the lithium metal is 10% to 70% based on 100% of the total mass of the carbon-lithium composite material.
35. A negative electrode, characterized in that the negative electrode comprises the porous carbon microsphere of any one of claims 1-11 and/or the carbon lithium composite of claim 33 or 34.
36. A lithium metal battery comprising the negative electrode of claim 35.
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