CN114122342A - Composite negative electrode material, preparation method thereof and lithium ion battery - Google Patents
Composite negative electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN114122342A CN114122342A CN202010899734.3A CN202010899734A CN114122342A CN 114122342 A CN114122342 A CN 114122342A CN 202010899734 A CN202010899734 A CN 202010899734A CN 114122342 A CN114122342 A CN 114122342A
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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Images
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- H01M4/00—Electrodes
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a composite negative electrode material, a preparation method thereof and a lithium ion battery. The composite negative electrode material comprises nano active particles, a graphite carbon material and a binder, wherein the binder is dispersed on the surface of the nano active particles, the nano active particles comprise metal nano particles and a nano protective layer formed on the surface of the metal nano particles, and the binder comprises at least one of a phosphate-based adhesive and a conductive silver adhesive. The problems that the silicon cathode material in the prior art is poor in expansion and cycle performance, relatively high in absolute value, incapable of being applied to batteries with strict requirements on expansion volume, such as soft-package batteries, and incapable of meeting the requirements of next-generation battery materials on ultra-long cycle and low expansion are solved.
Description
Technical Field
The invention belongs to the field of electrochemistry and the field of application of lithium ion battery cathode materials, and relates to a composite material, a preparation method and a lithium ion battery containing the composite material.
Background
Currently, with the development of new energy vehicles, the demand for high energy density cathode materials is continuously increased, wherein silicon cathodes are generally regarded as the cathode materials of next generation batteries, and have the advantages of high capacity, rich sources, relative safety and the like. However, the silicon negative electrode has a violent volume expansion effect in the circulating process, so that the material is pulverized and broken, and the cycle decay of the battery is rapid. To solve this problem, there are multiple solutions at present, including structural design of silicon, using nanocrystallization, porosification, composite coating, or using new electrolyte and additive to improve in the preparation of battery.
A lithium battery silicon negative electrode composite material comprises nanometer silicon and graphite, wherein a lithium silicate nanometer protective layer is formed on the surface of the nanometer silicon. In the lithium battery silicon negative electrode composite material, the lithium silicate nano protective layer is formed on the surface of the nano silicon to improve the stability between the nano silicon and the electrolyte interface and inhibit the expansion of the silicon core.
However, the lithium silicate nano protective layer structure is easily damaged during the cycle of the lithium battery silicon negative electrode composite material, and the lithium silicate nano protective layer structure is damaged, so that the nano silicon expands to pulverize the lithium battery silicon negative electrode composite material, thereby causing poor cycle performance.
Disclosure of Invention
Based on the above, there is a need for a low-expansion, long-cycle composite negative electrode material, a preparation method thereof, and a lithium ion battery.
In a first aspect, a composite anode material is provided, where the composite anode material includes a nano active particle, a graphite-based carbon material, and a binder, the binder is dispersed on the surface of the nano active particle, the nano active particle includes a metal nanoparticle and a nano protective layer formed on the surface of the metal nanoparticle, and the binder includes at least one of a phosphate-based adhesive and a conductive silver adhesive.
Preferably, the binder is distributed between the nano active particles and the graphite-like carbon material, and/or the binder is distributed on the surface of the graphite-like carbon material.
Preferably, the phosphate-based adhesive contains phosphate.
Preferably, the phosphate comprises at least one of aluminum dihydrogen phosphate, aluminum dihydrogen pyrophosphate, and aluminum dihydrogen metaphosphate.
Preferably, the phosphate-based adhesive further comprises alumina.
Preferably, in the phosphate-based adhesive, the mass ratio of the phosphate to the alumina is (10-80): 0-10.
Preferably, the median particle diameter of the nano-active particles is 1nm to 500 nm.
Preferably, the nano-active particles have a specific surface area of 1m2/g～500m2/g。
Preferably, the nano-active particles are distributed between the graphite-like carbon materials and/or the nano-active particles are distributed on the surface of the graphite-like carbon materials.
Preferably, the nano-active particles comprise metal nanoparticles.
Preferably, the metal nanoparticles include at least one of lithium, silicon, germanium, tin, nickel, iron, cobalt, magnesium, aluminum, and copper.
Preferably, the median particle diameter of the metal nanoparticles is 1nm to 300 nm.
Preferably, the nano protective layer is formed in situ on the surface of the metal nanoparticles.
Preferably, the nano-sized protective layer includes at least one of aluminum oxide, silicon oxide, zinc oxide, titanium oxide, manganese oxide, copper oxide, cobalt oxide, silicate, phosphate, titanate, and lithium oxide.
Preferably, the thickness of the nano protective layer is 1nm to 30 nm.
Preferably, the graphite-based carbon material includes at least one of artificial graphite, natural graphite, and mesocarbon microbeads.
Preferably, the median particle diameter of the graphitic carbon material is 1 μm to 25 μm.
Preferably, the mass ratio of the nano active particles to the graphite-based carbon material is (0.5-5): 1.
Preferably, the mass ratio of the binder to the nano active particles is (0.01-0.08): 1.
Preferably, the mass content of the nano active particles is 10% to 60% based on 100% by mass of the composite anode material.
Preferably, the specific surface area of the composite anode material is 1m2/g～30m2/g。
Preferably, the powder compaction density of the composite negative electrode material is 0.5g/cm3～2g/cm3。
Preferably, the median particle diameter of the composite anode material is 1 μm to 45 μm.
Preferably, the composite negative electrode material is of a core-shell structure, the core of the core-shell structure comprises the graphite carbon material, the nano active particles and the binder, and the shell of the core-shell structure is a carbon coating layer.
Preferably, the thickness of the carbon coating layer is 5nm to 1000 nm.
In a second aspect, a method for preparing a composite anode material is provided, which comprises the following steps:
forming a nano protective layer on the surface of the metal nano particle to obtain nano active particles; and
mixing the nano active particles, the binder and the graphite carbon material in an organic solvent, drying and sintering to obtain the composite negative electrode material;
wherein the binder comprises at least one of a phosphate-based adhesive and a conductive silver adhesive.
In some possible embodiments, the method of forming the nano protective layer includes at least one of an oxidation reaction method, a reduction reaction method, and a physical coating method.
Preferably, the method of forming a nano protective layer includes: carrying out oxidation reaction on the surface of the metal nano-particle to form an oxide layer, wherein the oxide layer is a nano-protective layer;
preferably, the method of forming a nano protective layer includes: and carrying out oxidation reaction on the surface of the metal nano particle to form an oxide layer, and reducing the oxide layer by adopting a metal simple substance to form the nano protective layer.
Preferably, the metal simple substance comprises at least one of K, Na, Mg, Zn, Ca, Li, Rb and Ce.
Preferably, the organic solvent includes at least one of tetrahydrofuran, amides, alcohols, and ketones.
Preferably, the organic solvent comprises at least one of tetrahydrofuran, dimethylacetamide, C1-C6 alcohols, and C3-C8 ketones.
Preferably, the C1-C6 alcohol includes at least one of methanol, ethanol, ethylene glycol, propanol, isopropanol, 1, 2-propanediol, 1, 3-propanediol, glycerol, n-butanol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, n-pentanol, and 2-hexanol.
Preferably, the C3-C8 ketone includes at least one of acetone, methyl ethyl ketone, methyl propyl ketone, N-methyl pyrrolidone, ethyl propyl ketone, methyl butyl ketone, ethyl N-butyl ketone, methyl amyl ketone, and methyl hexyl ketone.
Preferably, the mixing further comprises: mixing the nano active particles, the binder, the dispersant and the graphite-like carbon material in an organic solvent.
Preferably, the dispersant includes at least one of a silane coupling agent, n-octadecanoic acid, epoxy resin, lauric acid, polyacrylic acid, sodium dodecylbenzenesulfonate, n-eicosanoic acid, polyvinyl chloride, and polyvinyl pyrrolidone.
Preferably, the mass ratio of the graphite-like carbon material, the organic solvent and the dispersant is (5-50): (50-200): (0.05-0.5).
Preferably, the method of drying comprises at least one of vacuum drying, spray drying and rotary evaporation.
Preferably, the method further comprises the step of forming a carbon coating layer: and mixing the dried product with a coated carbon source, and sintering to obtain the composite anode material.
Preferably, the coated carbon source comprises at least one of epoxy resin, citric acid, sucrose, glucose, asphalt, phenolic resin, fructose, polyethylene glycol, polyvinyl alcohol, and polyvinyl chloride.
Preferably, the sintering temperature is 500-1500 ℃.
Preferably, the sintering time is 1-12 h.
Preferably, the sintering is performed under a protective atmosphere whose gas includes at least one of nitrogen, helium, neon, argon, krypton, and xenon.
Preferably, the method comprises the steps of:
carrying out oxidation reaction on the surface of the metal nano-particles to obtain nano active particles;
or carrying out oxidation reaction on the surface of the metal nano-particles to form an oxide layer, and reducing the oxide layer by adopting a metal monomer to obtain nano active particles;
mixing the nano active particles, a dispersing agent, a binder and a graphite carbon material in an organic solvent, and drying to obtain a precursor, wherein the binder comprises at least one of a phosphate-based adhesive and a conductive silver adhesive; and
and mixing the precursor with a coated carbon source, and sintering to obtain the composite anode material.
In a third aspect, a lithium ion battery is provided, which includes the composite negative electrode material of the first aspect.
The lithium ion battery provided by the third aspect has the advantages of low expansion rate of the pole piece and good cycling stability.
Compared with the prior art, the technical scheme at least has the following beneficial effects:
in the technical scheme, the nano protective layer is formed on the surface of the nano silicon particles, so that the volume expansion of the silicon core is inhibited, and the active substance is prevented from being directly contacted with the electrolyte to form a stable SEI film. The adopted binder can resist high temperature, does not lose efficacy through subsequent carbonization treatment, and has good binding effect, the phosphate-based adhesive and the conductive silver adhesive are dispersed on the surface of the nano active particles as the binder, so that the nano protective layer can be stabilized, the structural damage of the nano protective layer in the circulation process is avoided, meanwhile, the nano active particles are bonded with the graphite carbon material through the powerful binder, the structural stability of the nano active particles and the graphite carbon material is improved, the expansion of the nano active particles is better inhibited, the pulverization and the structural damage in the volume change process of the composite cathode material are avoided, and the circulation performance is greatly improved. Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) picture of the nano silicon-based composite anode material prepared in example 1 of the present invention.
Fig. 2 is an XRD pattern of the nano silicon-based composite anode material prepared in example 1 of the present invention.
Fig. 3 is a first charge-discharge curve of the nano silicon-based composite anode material prepared in example 1 of the present invention.
Fig. 4 is a cycle performance curve of the nano silicon-based composite anode material prepared in example 1 of the present invention.
Fig. 5 is a process flow chart of a preparation method of the composite anode material according to the embodiment of the invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other. Without departing from the principles of embodiments of the present invention, several modifications and refinements may be made, and these are considered to be within the scope of the embodiments of the present invention.
An embodiment provides a composite negative electrode material, which is used for solving the problems that the silicon negative electrode material in the prior art has poor expansion and cycle performance and relatively high absolute value, cannot be applied to batteries with strict requirements on expansion volume, such as soft package batteries, and cannot meet the requirements of the next generation of battery materials on ultra-long cycle and low expansion. Another embodiment provides a method for preparing the composite anode material. Yet another embodiment provides a lithium ion battery comprising the composite anode material described above.
The composite negative electrode material of an embodiment comprises nano active particles, a graphite carbon material and a binder, wherein the surface of the nano active particles is dispersed with the binder, the nano active particles comprise metal nano particles and a nano protective layer formed on the surface of the metal nano particles, and the binder comprises at least one of a phosphate-based adhesive and a conductive silver adhesive.
In the above embodiment, the nano protective layer is formed on the surface of the nano silicon particle, and on one hand, the nano protective layer can inhibit the expansion of the silicon core, and on the other hand, the nano protective layer can avoid the direct contact of the active substance and the electrolyte, so that the stability of the SEI film is improved, and the electrochemical performance of the material is improved under the combined action of the two aspects. The thickness of the nanometer protective layer is adjustable, and the embedding and the releasing of lithium ions are influenced due to the fact that the nanometer protective layer is too thick. The binder stably exists at the preparation temperature (generally 500-1500 ℃) of the composite negative electrode material, the binder cannot lose effectiveness due to a sintering step in the preparation process of the composite negative electrode material, the binder has good binding effect, the binder is dispersed on the surface of the nano active particles, a nano protective layer can be stabilized, the structural damage of the nano protective layer in a circulation process is avoided, meanwhile, the binder enables the connection between the nano active particles and a graphite carbon material to be more stable, the nano active particles (such as nano silicon) are not easy to pulverize and fall off in the lithium intercalation/lithium deintercalation process, and the electrochemical performance is enhanced. The problems that the carbon coating structure in the prior art has limited effect on inhibiting expansion of materials such as silicon and the like, has relatively high absolute value, cannot be applied to batteries with strict requirements on expansion volume, such as soft-package batteries, and cannot meet the requirements of ultra-long circulation and low expansion of next-generation battery materials are solved.
In some embodiments, a binder is disposed between the nano-active particles and the graphitic carbon material, and/or a binder is disposed on the surface of the graphitic carbon material.
In some embodiments, phosphate-based adhesives, also referred to as phosphate-based binders, phosphate binders, include phosphate salts.
In some embodiments, the phosphate salt comprises at least one of aluminum dihydrogen phosphate, aluminum dihydrogen pyrophosphate, and aluminum dihydrogen metaphosphate.
In some embodiments, the phosphate-based binder further comprises alumina.
In some embodiments, the phosphate-based adhesive has a phosphate to alumina mass ratio of (10-80) to (0-10).
The matching degree of the adhesive with silicon and graphite is better, and the electrochemical performance of the silicon-carbon composite material is better improved.
In some embodiments, the nano-active particles have a median particle size of 1nm to 500nm, and more specifically, may be 1nm, 3nm, 5nm, 8nm, 10nm, 15nm, 20nm, 30nm, 45nm, 60nm, 80nm, 100nm, 120nm, 130nm, 150nm, 175nm, 200nm, 230nm, 260nm, 300nm, 320nm, 350nm, 370nm, 400nm, 450nm, or 500nm, and the like.
In some embodiments, the nano-active particles have a specific surface area of 1m2/g～500m2A/g, more particularly, may be 2m2/g、5m2/g、10m2/g、15m2/g、20m2/g、30m2/g、50m2/g、70m2/g、100m2/g、125m2/g、150m2/g、180m2/g、200m2/g、220m2/g、240m2/g、300m2/g、350m2/g、400m2G or 500m2And/g, etc.
In some embodiments, the nano-active particles are distributed between the graphitic carbon material and/or the nano-active particles are distributed on the surface of the graphitic carbon material.
In some embodiments, the binder binds the graphite-like carbon material to form a connector, and the nano active particles are embedded in the connector, so that the expansion of the nano active particles can be effectively avoided, and the cycle performance is improved.
In some embodiments, the nano-active particles comprise metal nanoparticles.
In some embodiments, the metal nanoparticles comprise at least one of lithium, silicon, germanium, tin, nickel, iron, cobalt, magnesium, aluminum, and copper. The structure of the composite anode material in these embodiments is particularly effective in suppressing the volume expansion of silicon.
In some embodiments, the metal nanoparticles have a median particle diameter of 1nm to 300nm, more specifically, 1nm, 5nm, 10nm, 15nm, 20nm, 40nm, 50nm, 60nm, 80nm, 100nm, 125nm, 150nm, 180nm, 200nm, 230nm, 245nm, 260nm, 280nm, or 300nm, etc., preferably 1nm to 150nm, and more preferably 2nm to 100 nm.
In some embodiments, the nano-protection layer is formed in situ on the surface of the metal nanoparticles. The protective layer is formed on the surface of the metal nano-particles in situ, so that the effect of improving the electrochemical performance can be better exerted. The prior art has the problems that the effective load cannot be effectively loaded and the metal nano particles are easy to fall off when the metal nano particles are directly adsorbed on the surfaces of the metal nano particles by a physical method, and the problems can be effectively solved by an in-situ forming mode.
In some embodiments, the nano-sized protective layer includes at least one of aluminum oxide, silicon oxide, zinc oxide, titanium oxide, manganese oxide, copper oxide, cobalt oxide, silicates, phosphates, titanates, and lithium oxide.
In some embodiments, the nano-sized protective layer has a thickness of 1nm to 30nm, and more specifically, may be 1nm, 2nm, 4nm, 6nm, 10nm, 15nm, 20nm, 25nm, 30nm, or the like.
In some embodiments, the graphitic carbon material comprises at least one of artificial graphite, natural graphite, and mesocarbon microbeads.
In some embodiments, the graphitic carbon material has a median particle size of 1 μm to 25 μm, and more specifically may be 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 20 μm, 25 μm, or the like.
In some embodiments, the mass ratio of the nano-active particles to the graphitic carbon material is (0.5-5): 1, and more specifically, may be 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 4:1, or 5:1, etc.
In some embodiments, the mass ratio of the binder to the nano-active particles is (0.01-0.08): 1, and more specifically, may be 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, or 0.08:1, and the like. Too little binder content results in poor binding effect and low silicon expansion control effect; too much binder content can lead to a reduction in the capacity of the material.
In some embodiments, the nano active particles may be included in an amount of 10% to 60% by mass, more specifically, 10%, 20%, 30%, 35%, 40%, 45%, 50%, 60%, or the like, based on 100% by mass of the composite anode material.
In some embodiments, the composite anode material has a specific surface area of 1m2/g～30m2A/g, more particularly, may be 1m2/g、3m2/g、5m2/g、10m2/g、13m2/g、16m2/g、20m2/g、22m2/g、25m2G or 30m2And/g, etc.
In some embodiments, the composite anode material has a powder compaction density of 0.5g/cm3～2g/cm3More specifically, it may be 0.5g/cm3、1g/cm3、1.2g/cm3、1.3g/cm3、1.5g/cm3、1.6g/cm3、1.8g/cm3Or 2g/cm3And the like.
In some embodiments, the composite anode material has a median particle diameter of 1 μm to 45 μm, and more specifically, may be 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, or 45 μm, and the like.
In some embodiments, the composite negative electrode material is a core-shell structure, the core of the core-shell structure includes a graphite-based carbon material, nano active particles and a binder, and the shell of the core-shell structure is a carbon coating layer.
In some embodiments, the carbon coating layer has a thickness of 5nm to 1000nm, and more specifically, may have a thickness of 6nm, 10nm, 15nm, 20nm, 30nm, 45nm, 60nm, 75nm, 90nm, 100nm, 120nm, 150nm, 180nm, 200nm, 235nm, 260nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 1000nm, or the like.
The preparation method of the composite anode material comprises the steps of S100-S300, and the process flow chart of the preparation method is shown in figure 5.
And S100, preparing the nano active particles.
In some embodiments, a method of preparing a nano-active particle comprises: and forming a nano protective layer on the surface of the metal nano particles.
In some embodiments, the nano-protection layer is formed by at least one of an oxidation reaction method, a reduction reaction method, and a physical coating method.
In some embodiments, preparing the nano-active particles specifically includes step S101 or step S102.
And S101, carrying out oxidation reaction on the surface of the metal nano-particles to obtain nano active particles.
And S102, performing oxidation reaction on the surface of the metal nano-particles to form an oxide layer, and reducing the oxide layer by adopting a metal monomer to obtain the nano active particles.
In some embodiments, the elemental metal comprises at least one of K, Na, Mg, Zn, Ca, Li, Rb, Ce.
It can be understood that, one of the steps S101 or S102 is selected to prepare the nano-active particles, for example, silicon is oxidized on the surface thereof to form silicon oxide, and then the silicon oxide is reduced by using lithium to form the nano-lithium silicate protective layer. For another example, the silicon may be oxidized to form silicon oxide on the surface thereof, and then the silicon oxide may be reduced by using aluminum to form the nano-alumina protective layer.
And S200, mixing the nano active particles, the binder and the graphite carbon material in an organic solvent, and drying to obtain a precursor.
In some embodiments, the organic solvent comprises at least one of tetrahydrofuran, amides, alcohols, and ketones, and more preferably at least one of tetrahydrofuran, dimethylacetamide, C1-C6 alcohols, and C3-C8 ketones.
In some embodiments, the C1-C6 alcohol is at least one of methanol, ethanol, ethylene glycol, propanol, isopropanol, 1, 2-propanediol, 1, 3-propanediol, glycerol, N-butanol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, N-pentanol, and 2-hexanol, and the C3-C8 ketone is at least one of acetone, methyl ethyl ketone, methyl propyl ketone, N-methyl pyrrolidone, ethyl propyl ketone, methyl butyl ketone, ethyl N-butyl ketone, methyl amyl ketone, and methyl hexyl ketone.
In some embodiments, the mixing process of step S200 further comprises adding a dispersant.
In some embodiments, the dispersant comprises at least one of a silane coupling agent, n-octadecanoic acid, epoxy, lauric acid, polyacrylic acid, sodium dodecylbenzenesulfonate, n-eicosanoic acid, polyvinyl chloride, and polyvinyl pyrrolidone.
In some embodiments, the mass ratio of the graphitic carbon material, the organic solvent, and the dispersant is (5-50): (50-200): (0.05-0.5), and more specifically, may be 5:100:0.1, 10:50:0.1, 20:100:0.2, 50:100:0.3, and the like.
In some embodiments, the method of drying is any one of vacuum drying, spray drying, or rotary evaporation.
And step S300, mixing the precursor with a coated carbon source, and sintering to obtain the composite negative electrode material.
The mixing method in the above embodiment is not limited, and more specifically, the mixing may be performed by using a VC machine and a fusion machine, and it is preferable that the VC machine is used to perform the VC mixing first, and then the fusion machine is used to perform the fusion. VC is mixed and then is subjected to re-fusion treatment, so that the mixing is more uniform, and meanwhile, the effective granulation treatment of particles can be carried out to form balls, and meanwhile, small particles are reduced.
In some embodiments, the coated carbon source comprises at least one of epoxy, citric acid, sucrose, glucose, pitch, phenolic, fructose, polyethylene glycol, polyvinyl alcohol, and polyvinyl chloride.
In some embodiments, the sintering temperature is 500 ℃ to 1500 ℃, more specifically 500 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1300 ℃, 1400 ℃, or 1500 ℃, etc., preferably 800 ℃ to 1100 ℃.
In some embodiments, the sintering time is 1h to 12h, more specifically, 1h, 3h, 5h, 7h, 8h, 10h, 12h, etc., preferably 3h to 10 h.
In some embodiments, the sintering is performed under a protective atmosphere whose gases include at least one of nitrogen, helium, neon, argon, krypton, and xenon.
In some embodiments, the sintering is performed in a reactor comprising any one of a vacuum furnace, a box furnace, a rotary furnace, a roller kiln, a pusher kiln, and a tube furnace.
It can be understood that the operation of carbon coating in step S300 may not be performed, that is, the obtained precursor is directly sintered to obtain the composite anode material, and no carbon coating layer is formed on the surface of the obtained composite anode material.
The preparation method of the composite cathode material provided by the embodiment is simple and low in cost, and solves the problems that the preparation process of the cathode material in the prior art is complicated and the preparation cost is high.
A lithium ion battery comprising the composite anode material is provided. The cathode material in the lithium ion battery can be the composite cathode material; one part of the composite anode material can be the anode material disclosed in the prior art, and the other part of the composite anode material can be the anode material disclosed in the prior art.
The lithium ion battery provided by the embodiment has the advantages of low expansion rate and good cycle stability.
Example 1
Dispersing nano Si with the median particle size of 20nm in ethylene glycol, stirring, and adding H with the mass fraction of 5%2O2Stirring the solution for 4h to obtain Si @ SiO containing an oxide layer2Nanoparticles of SiO2The thickness of the layer was 8nm (wherein Si @ SiO was mentioned2The nano particle represents that the inner core is Si and the coating layer is SiO2The following examples and comparative examples represent the same meanings).
The above Si @ SiO2Nanoparticles, graphite having a median particle diameter of 10 μm, polyacrylic acid, and a binder (including aluminum dihydrogen phosphate) were dispersed in a mixed solvent of water and ethanol, wherein water: the weight ratio of the ethanol is 10:90, the weight ratio of the graphite, the polyacrylic acid and the binder is 2:3, the mixture is uniformly stirred and then dried to obtain a precursor.
And (2) proportioning the precursor powder and glucose with the particle size of 5 microns according to the mass ratio of 20:80, carrying out VC mixing with the mixing parameter of frequency 25HZ and time 40min, adding into a fusion machine, adjusting the rotating speed to 400rpm, fusing for 0.45h, placing into a box-type furnace, introducing nitrogen protective gas, heating to 800 ℃, keeping the temperature for 5h, and cooling to room temperature to obtain the silicon-based composite anode material, namely the nano silicon-based composite anode material.
The obtained silicon-based composite material comprises Si @ SiO2Nano particles, graphite, a binder (comprising aluminum dihydrogen phosphate) and a carbon coating layer on the surface. Si @ SiO2Nanoparticles distributed on the surface of graphite and between the graphites, Si @ SiO2The thickness of the nano protective layer on the surface layer of the nano particles is 8nm, Si @ SiO2The median particle diameter of the nanoparticles was 28 nm. The binder (comprising aluminum dihydrogen phosphate) is distributed in Si @ SiO2Between the nanoparticles and the graphite. Si @ SiO, based on 100% by mass of the obtained silicon-based composite material2The mass fraction of the nano particles is 45%, the mass fraction of the graphite is 27.3%, the mass fraction of the binder (including aluminum dihydrogen phosphate) is 2.7%, and the mass fraction of the carbon coating layer is 28%.
Fig. 1 is a Scanning Electron Microscope (SEM) picture of the nano silicon-based composite anode material prepared in example 1 of the present invention.
Fig. 2 is an XRD pattern of the nano silicon-based composite anode material prepared in example 1 of the present invention, from which it can be observed that there are silicon peaks and graphite peaks in the product.
Example 2
Placing the nano Ge particles with the median particle size of 100nm in a heat treatment furnace, introducing air, heating to 500 ℃, and preserving heat for 30min to obtain Ge @ GeO containing an oxide layer2Nanoparticles, GeO2The thickness of the layer was 15 nm.
Adding the Ge @ GeO2Nanoparticles, graphite having a median particle diameter of 1 μm, polyvinyl chloride, and a binder (the binder includes aluminum dihydrogen phosphate) were dispersed in a mixed solvent of water and ethanol, wherein water: the weight ratio of the ethanol is 20:80, the weight ratio of the graphite to the polyvinyl chloride to the binder is 94:3:3, the mixture is uniformly stirred and then dried to obtain the precursor.
Proportioning the precursor powder and phenolic resin with the particle size of 6 mu m according to the mass ratio of 20:20, then carrying out VC mixing, wherein the mixing parameter is frequency of 20HZ and time of 70min, then adding the mixture into a fusion machine, adjusting the rotating speed to 400rpm, fusing for 0.5h, then placing the mixture into a box-type furnace, introducing nitrogen protective gas, heating to 900 ℃, preserving heat for 5h, and cooling to room temperature to obtain the germanium-based composite material;
the obtained germanium-based composite material comprises Ge @ GeO2Nano particles, graphite, a binder (comprising aluminum dihydrogen phosphate) and a carbon coating layer on the surface. Ge @ GeO2Nanoparticles distributed on the surface of graphite and between graphites, Ge @ GeO2Nanoparticle surface layer GeO2The thickness of the layer is 15nm, Ge @ GeO2The median particle diameter of the nanoparticles was 115 nm. Binder distributed in Ge @ GeO2Between the nano-particles and the graphite. Based on the mass of the obtained germanium-based composite material as 100 percent, Ge @ GeO2The mass fraction of the nano particles is 33%, the mass fraction of the graphite is 42.4%, the mass fraction of the binder (including aluminum dihydrogen phosphate) is 1.6%, and the mass fraction of the carbon coating layer is 23%.
Example 3
Dispersing nano Si with the median particle size of 50nm in acetone, stirring, and then adding 5% of H2O2Stirring the solution for 4h to obtain Si @ SiO containing an oxide layer2Then mixing lithium metal, heating to 800 ℃ under the argon protective atmosphere, and preserving heat for 3h to obtain the lithium silicate coated nano silicon particles, wherein the thickness of the lithium silicate layer is 10 nm.
Dispersing the lithium silicate-coated nano silicon particles, graphite with a median particle size of 15 mu m, sodium dodecyl benzene sulfonate and a binder (the binder comprises aluminum dihydrogen phosphate and phosphoric acid, wherein the mass ratio of the aluminum dihydrogen phosphate to the phosphoric acid is 55: 10) into a mixed solvent of water and ethanol, the weight ratio of the water to the ethanol is 15:85, and the weight ratio of the graphite to the sodium dodecyl benzene sulfonate to the binder is 94:2:4, uniformly stirring, and then carrying out spray drying to obtain a precursor.
Mixing the powder and asphalt with the particle size of 8 mu m according to the mass ratio of 40:60, then carrying out VC mixing, wherein the mixing parameter is frequency of 30HZ and time is 60min, then adding the mixture into a fusion machine, adjusting the rotating speed to 300rpm, fusing for 1h, then placing the mixture into a box type furnace, introducing nitrogen protective gas, heating to 950 ℃, preserving heat for 3h, and cooling to room temperature to obtain the silicon-based composite material;
the obtained silicon-based composite material comprises lithium silicate-coated nano silicon particles, graphite, a binder (comprising aluminum dihydrogen phosphate) and a carbon coating layer on the surface. The lithium silicate-coated nano silicon particles are distributed on the surface of the graphite and among the graphite, the thickness of a lithium silicate layer on the surface layer of the lithium silicate-coated nano silicon particles is 10nm, and the median particle size of the lithium silicate-coated nano silicon particles is 60 nm. The binder is distributed between the lithium silicate-coated nano silicon particles and the graphite. Based on the mass of the obtained silicon-based composite material as 100%, the mass fraction of the lithium silicate-coated nano silicon particles is 55%, the mass fraction of the graphite is 10.8%, the mass fraction of the binder (including aluminum dihydrogen phosphate) is 3.2%, and the mass fraction of the carbon coating layer is 33%.
Example 4
Dispersing nanometer Sn with a median particle size of 100nm in n-butanol, stirring, and adding 5% of H2O2Stirring the solution for 1h to obtain Sn @ SnO containing an oxide layer2Nanoparticles, SnO2The thickness of the layer was 10 nm.
The Sn @ SnO2Nanoparticles, graphite having a median particle diameter of 5 μm, sodium dodecylbenzenesulfonate, and a binder (the binder includes aluminum dihydrogen pyrophosphate, aluminum dihydrogen phosphate, wherein aluminum dihydrogen phosphate: water: 25:35) were dispersed in a mixed solvent of water and ethanol, wherein water: the weight ratio of the ethanol is 30:70, the weight ratio of the graphite to the sodium dodecyl benzene sulfonate to the binder is 94:2.5:3.5, the mixture is uniformly stirred and then dried to obtain the precursor.
Proportioning the precursor powder and sucrose with the particle size of 10 mu m according to the mass ratio of 30:70, then carrying out VC mixing, wherein the mixing parameter is frequency of 30HZ and time is 20min, then adding the mixture into a fusion machine, adjusting the rotating speed to 400rpm, fusing for 1h, then placing the mixture into a box furnace, introducing nitrogen protective gas, heating to 850 ℃, keeping the temperature for 6h, and cooling to room temperature to obtain the tin-based composite material;
the obtained Sn-based composite material comprises Sn @ SnO2Nano particles, graphite, a binder (comprising aluminum dihydrogen phosphate) and a carbon coating layer on the surface. Sn @ SnO2Nanoparticles distributed on the surface of and between the graphites, Sn @ SnO2Nano particle surface SnO2The thickness of the layer is 10nm, Sn @ SnO2The median particle diameter of the nanoparticles was 110 nm. The binder is distributed in Sn @ SnO2Between the nanoparticles and the graphite. Si @ SiO in an amount of 100% by mass of the Sn-based composite material2The mass fraction of the nano particles is 49%, the mass fraction of the graphite is 31%, the mass fraction of the binder is 3%, and the mass fraction of the carbon coating layer is 17%.
Example 5
Dispersing nanometer Si with median particle diameter of 50nm in propanol, stirring, and mixingPost-addition of 5% H2O2Stirring the solution for 4h to obtain Si @ SiO containing an oxide layer2Then mixing metal aluminum, heating to 700 ℃ under the argon protective atmosphere, and preserving heat for 4 hours to obtain aluminum oxide coated nano silicon particles, Al2O3The thickness of the layer was 8 nm.
Dispersing the alumina-coated nano silicon particles, graphite with a median particle size of 10 μm, n-eicosanoic acid and a binder (the binder comprises aluminum dihydrogen metaphosphate) into a mixed solvent of water and propanol, wherein the weight ratio of water: the weight ratio of the propanol is 10:90, the weight ratio of the graphite, the n-eicosanoic acid and the binder is 93:2.5:4.5, the mixture is uniformly stirred and then dried to obtain the precursor.
Proportioning the precursor powder and phenolic resin with the particle size of 5 mu m according to the mass ratio of 40:60, then carrying out VC mixing, wherein the mixing parameter is frequency of 20HZ and time of 50min, then adding into a fusion machine, adjusting the rotating speed to 300rpm, fusing for 1h, then placing into a box furnace, introducing nitrogen protective gas, heating to 950 ℃, preserving heat for 4h, and cooling to room temperature to obtain the silicon-based composite material;
the obtained silicon-based composite material comprises Si @ SiO2Nano particles, graphite, a binder and a carbon coating layer on the surface. Si @ SiO2The nano particles are distributed on the surface of the graphite and among the graphite, and the surface layer Al of the nano silicon particles coated by the aluminum oxide2O3The thickness of the layer was 8nm, Si @ SiO2The median particle diameter of the nanoparticles was 58 nm. The binder is distributed in Si @ SiO2Between the nanoparticles and the graphite. Si @ SiO, based on 100% by mass of the obtained silicon-based composite material2The mass fraction of the nano particles is 41%, the mass fraction of the graphite is 19.3%, the mass fraction of the binder is 2.2%, and the mass fraction of the carbon coating layer is 37.5%.
Example 6
Dispersing nanometer Co with median particle diameter of 100nm in acetone, stirring, and adding 5% H2O2Stirring the solution for 4h to obtain Co @ Co containing an oxide layer2O3Nanoparticles, the oxide thickness was 20 nm.
Mixing the above Co @ Co2O3Nanoparticles, graphite having a median particle diameter of 8 μm, lauric acid, and a binder (the binder includes aluminum dihydrogen phosphate, phosphoric acid, in which aluminum dihydrogen metaphosphate is present in a weight ratio of 46:5) are dispersed in a mixed solvent of water and butanol, wherein water: the weight ratio of the butanol is 25:75, the weight ratio of the graphite to the lauric acid to the binder is 93.5:3:3.5, the mixture is uniformly stirred and then dried to obtain the precursor.
Proportioning the powder and asphalt with the particle size of 8 mu m according to the mass ratio of 40:60, then carrying out VC mixing with the mixing parameter of 40HZ for 10min, then adding into a fusion machine, adjusting the rotating speed to 500rpm, fusing for 1h, then placing into a box furnace, introducing nitrogen protective gas, heating to 850 ℃, preserving heat for 3h, and cooling to room temperature to obtain the cobalt-based composite material;
the obtained cobalt-based composite material comprises Co @ Co2O3Nano particles, graphite, a binder and a carbon coating layer on the surface. Co @ Co2O3Nanoparticles distributed on the surface of graphite and between the graphites, Co @ Co2O3The thickness of the top oxide of the nanoparticles was 20nm, Co @ Co2O3The median particle diameter of the nanoparticles was 120 nm. Binder (including aluminum dihydrogen phosphate) distributed in Co @ Co2O3Between the nanoparticles and the graphite. Based on the mass of the obtained cobalt-based composite material as 100 percent, Co @ Co2O3The mass fraction of the nano particles is 35%, the mass fraction of the graphite is 29%, the mass fraction of the binder (including aluminum dihydrogen phosphate) is 5%, and the mass fraction of the carbon coating layer is 31%.
Example 7
A nano silicon-based composite anode material was prepared in substantially the same manner as in example 1, except that: no nano protective layer is formed on the surface of the nano silicon particles.
The obtained silicon-based composite material comprises Si nano particles, graphite, a binder (comprising aluminum dihydrogen phosphate) and a carbon coating layer on the surface. The Si nano particles are distributed on the surface of the graphite and among the graphite, and the median particle size of the Si nano particles is 20 nm. A binder (comprising aluminum dihydrogen phosphate) is distributed between the Si nanoparticles and the graphite. Based on the mass of the obtained silicon-based composite material as 100%, the mass fraction of the Si nano particles is 45%, the mass fraction of the graphite is 27.3%, the mass fraction of the binder (including aluminum dihydrogen phosphate) is 2.7%, and the mass fraction of the carbon coating layer is 28%.
Example 8
Dispersing nano Si with the median particle size of 70nm in ethylene glycol, stirring, and adding H with the mass fraction of 2%2O2Stirring the solution for 4h to obtain Si @ SiO containing an oxide layer2Nanoparticles of SiO2The thickness of the layer was 5 nm.
The above Si @ SiO2Nano particles, graphite with a median particle size of 10 mu m, polyacrylic acid and conductive silver colloid (which comprises Ag powder and phenolic resin in a weight ratio of 80:20) are dispersed in a mixed solvent of water and methanol, wherein the weight ratio of water: the weight ratio of the methanol is 35:65, wherein the weight ratio of the graphite to the polyacrylic acid to the conductive silver adhesive is 95:2:3, the mixture is uniformly stirred, and then the precursor is obtained after drying.
And (2) proportioning the precursor powder and glucose with the particle size of 10 microns according to the mass ratio of 20:80, carrying out VC mixing with the mixing parameter of 35HZ for 60min, then adding into a fusion machine, adjusting the rotating speed to 400rpm, fusing for 0.45h, then placing into a box-type furnace, introducing nitrogen protective gas, heating to 800 ℃, keeping the temperature for 5h, and cooling to room temperature to obtain the silicon-based composite anode material, namely the nano silicon-based composite anode material.
The obtained silicon-based composite material comprises Si @ SiO2Nano particles, graphite, a binder and a carbon coating layer on the surface. Si @ SiO2The nano particles are distributed on the surface of the graphite and among the graphite. Si @ SiO2Surface layer SiO of nano particle2The thickness of the layer was 5nm, Si @ SiO2The median particle diameter of the nanoparticles was 75 nm. The binder is distributed in Si @ SiO2Between the nanoparticles and the graphite. Si @ SiO, based on 100% by mass of the obtained silicon-based composite material2The mass fraction of the nano particles is 51%, the mass fraction of the graphite is 23.6%, the mass fraction of the binder is 3.4%, and the mass fraction of the carbon coating layer is 22%.
Example 9
Dispersing nano Si with the median particle size of 80nm in butanol, stirring, and adding H with the mass fraction of 3%2O2Stirring the solution for 4h to obtain Si @ SiO containing an oxide layer2Nanoparticles of SiO2The thickness of the layer was 10 nm.
The above Si @ SiO2Nano particles, graphite with a median particle size of 10 mu m, polyacrylic acid and a binder (which comprises aluminum dihydrogen phosphate, Ag powder and phenolic resin in a weight ratio of 55:40:10) are dispersed in a mixed solvent of water and amyl alcohol, wherein the weight ratio of water: amyl alcohol is in a weight ratio of 10:90, wherein the weight ratio of the graphite to the polyacrylic acid to the binder is 94:2.5:3.5, the mixture is uniformly stirred, and then the precursor is obtained after drying.
And (2) proportioning the precursor powder and glucose with the particle size of 10 microns according to the mass ratio of 20:80, carrying out VC mixing with the mixing parameter of frequency 25HZ and time 80min, adding into a fusion machine, adjusting the rotating speed to 400rpm, fusing for 0.45h, placing into a box-type furnace, introducing nitrogen protective gas, heating to 800 ℃, keeping the temperature for 5h, and cooling to room temperature to obtain the silicon-based composite anode material, namely the nano silicon-based composite anode material.
The obtained silicon-based composite material comprises Si @ SiO2Nano particles, graphite, a binder and a carbon coating layer on the surface. Si @ SiO2The nano particles are distributed on the surface of the graphite and among the graphite. Si @ SiO2SiO of nanoparticles2The thickness of the layer was 10nm, Si @ SiO2The median particle diameter of the nanoparticles was 90 nm. The binder is distributed in Si @ SiO2Between the nanoparticles and the graphite. Si @ SiO, based on 100% by mass of the obtained silicon-based composite material2The mass fraction of the nano particles is 41%, the mass fraction of the graphite is 33%, the mass fraction of the binder is 1.4%, and the mass fraction of the carbon coating layer is 24.6%.
Example 10
The fusion step was not performed, but heat-treated directly in a box furnace, and other preparation methods and conditions were the same as in example 1.
The obtained silicon-based composite material comprises Si @ SiO2Nanoparticles, graphite, binders (including aluminum dihydrogen phosphate) and watchA carbon coating of the face. Si @ SiO2The thickness of the nano protective layer on the surface layer of the nano particles is 8nm, Si @ SiO2The median particle diameter of the nanoparticles was 28 nm. Si @ SiO, based on 100% by mass of the obtained silicon-based composite material2The mass fraction of the nano particles is 45%, the mass fraction of the graphite is 27.3%, the mass fraction of the binder (including aluminum dihydrogen phosphate) is 2.7%, and the mass fraction of the carbon coating layer is 28%.
Example 11
The precursor powder was directly subjected to the fusion step with glucose without VC mixing, and other preparation methods and conditions were the same as in example 1.
The obtained silicon-based composite material comprises Si @ SiO2Nano particles, graphite, a binder (comprising aluminum dihydrogen phosphate) and a carbon coating layer on the surface. Si @ SiO2The thickness of the nano protective layer on the surface layer of the nano particles is 8nm, Si @ SiO2The median particle diameter of the nanoparticles was 28 nm. Si @ SiO, based on 100% by mass of the obtained silicon-based composite material2The mass fraction of the nano particles is 45%, the mass fraction of the graphite is 27.3%, the mass fraction of the binder (including aluminum dihydrogen phosphate) is 2.7%, and the mass fraction of the carbon coating layer is 28%.
Example 12
The difference from example 1 is that no carbon coating layer is included.
The obtained silicon-based composite material comprises Si @ SiO2Nano particles, graphite, a binder (comprising aluminum dihydrogen phosphate) and a carbon coating layer on the surface. Si @ SiO2Nanoparticles distributed on the surface of graphite and between the graphites, Si @ SiO2The thickness of the nano protective layer on the surface layer of the nano particles is 8nm, Si @ SiO2The median particle diameter of the nanoparticles was 28 nm. The binder (comprising aluminum dihydrogen phosphate) is distributed in Si @ SiO2Between the nanoparticles and the graphite. Si @ SiO, based on 100% by mass of the obtained silicon-based composite material2The mass fraction of the nano particles is 60%, the mass fraction of the graphite is 36.4%, and the mass fraction of the binder (including aluminum dihydrogen phosphate) is 3.6%.
Example 13
The difference from example 1 is that the binder includes both conductive silver paste and phosphate-based adhesive, the amount of the binder used in this embodiment is the same as that in example 1, the phosphate-based adhesive in this embodiment is the same as that in example 1, the conductive silver paste in this embodiment includes Ag powder and epoxy resin, the mass ratio of the conductive silver paste to the phosphate-based adhesive in this embodiment is 20:80, and the mass ratio of the conductive silver paste to the phosphate-based adhesive in this embodiment is 55: 45.
The obtained silicon-based composite material comprises Si @ SiO2The nano-particle graphite coating comprises nano-particles, graphite, a binder (comprising conductive silver adhesive and phosphate-based adhesive, wherein the mass ratio of the conductive silver adhesive to the phosphate-based adhesive is 55:45) and a carbon coating layer on the surface. Si @ SiO2Nanoparticles distributed on the surface of graphite and between the graphites, Si @ SiO2The thickness of the nano protective layer on the surface layer of the nano particles is 8nm, Si @ SiO2The median particle diameter of the nanoparticles was 28 nm. The binder is distributed in Si @ SiO2Between the nanoparticles and the graphite. Si @ SiO, based on 100% by mass of the obtained silicon-based composite material2The mass fraction of the nano particles is 45%, the mass fraction of the graphite is 27.3%, the mass fraction of the binder (including conductive silver adhesive and phosphate-based binder) is 2.7%, and the mass fraction of the carbon coating layer is 28%.
Comparative example 1
A nano silicon-based composite anode material was prepared in substantially the same manner as in example 1, except that: no binder was added during the precursor preparation, and the other preparation methods and conditions were the same as in example 1.
Comparative example 2
A nano silicon-based composite anode material was prepared in substantially the same manner as in example 1, except that: PVDF was added as a binder in the precursor preparation process, and other preparation methods and conditions were the same as in example 1.
Electrochemical cycling performance was tested using the following method: dissolving the negative electrode material, the conductive agent and the binder in a solvent according to the mass percentage of 94:1:5, mixing, controlling the solid content to be 50%, coating the mixture on a copper foil current collector, and drying in vacuum to obtain a negative electrode plate; then preparing a ternary positive pole piece prepared by a traditional mature process and 1mol/L LiPF6Electrolyte of/EC + DMC + EMC (v/v ═ 1:1:1), Celgard2The 400 diaphragm, housing, used a conventional manufacturing process to assemble 18650 cylindrical cell. The charge and discharge test of the cylindrical battery is carried out on a LAND battery test system of Wuhanjinnuo electronic Limited company, and the charge and discharge voltage is limited to 2.75V-4.2V at the constant current of 0.2C under the normal temperature condition.
Fig. 3 is a first charge-discharge curve of the nano silicon-based composite anode material prepared in example 1 of the present invention, and it can be seen from the graph that the material has a higher first charge-discharge capacity and a higher first efficiency.
Fig. 4 is a cycle performance curve of the nano silicon-based composite anode material prepared in example 1 of the present invention, and it can be seen from the graph that the material has excellent cycle performance, and the capacity retention rate is 93.1% after 100 cycles.
TABLE 1
As can be seen from the above table, the composite anode material prepared by coating the protective layer on the metal nanoparticles such as silicon and introducing the specific binder has a low specific surface area (3.0 m)2/g～5.0m2The discharge capacity is high (more than 1000mAh/g), the first coulombic efficiency is high (more than 88%), and the capacity retention rate is more than 92.5% after 100 cycles.
In example 7, the silicon is not coated with the protective layer, so that the capacity retention rate of the obtained composite anode material is only 80.3% after the anode material is cycled for 100 weeks. In the preparation process of comparative example 1, no binder is used, so that the first efficiency of the composite anode material is only 84.1%, and the capacity retention rate of the composite anode material after 100 cycles is only 84.1%. Therefore, the protective layer and the binder in the composite negative electrode material have unexpected technical effects on effect improvement.
In comparison with example 10, it is seen that the sample not subjected to the fusion treatment has increased small particles, and further increased the specific surface area of the material, and thus the first efficiency was low and the cycle performance was slightly lowered.
As is clear from comparison between example 1 and example 11, since the active material and the carbon source material are not uniformly dispersed without VC mixing, the carbon coating effect is deteriorated in the carbonization process, the specific surface area of the material is increased, the conductivity is reduced, the first efficiency is low, and the cycle is worse.
The composite material of example 1 had a 50-cycle expansion rate of 37%, and the composite material of comparative example 1 had an expansion rate of 49.2% using a common silicon particle.
In comparison between example 1 and example 12, the specific surface area of the material is significantly increased without the surface coating layer, and during the circulation process, silicon is in direct contact with the electrolyte, which results in reduced first effect and poor circulation performance.
Comparing example 1 with example 13, the materials prepared by using two binders have slightly better cycle performance and first-effect performance, because the conductive silver colloid has improved conductivity and is beneficial to electron transmission.
Comparing example 1 with comparative example 1, it is clear that the expansion of silicon is not restrained without using a binder, and thus the expansion of the material is large and the cycle is poor.
Comparing example 1 with comparative example 2, it can be seen that some conventional binders fail after high temperature carbonization treatment, do not have a bonding effect, and have a similar effect to that of the binders, and cannot restrict the expansion of silicon, so that the expansion of the material is large, and the cycle is poor.
The invention is applicable to silicon-based materials, and also applicable to other metal negative electrodes such as Ge, Sn-based materials and the like.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The composite negative electrode material is characterized by comprising nano active particles, a graphite carbon material and a binder, wherein the binder is dispersed on the surfaces of the nano active particles, the nano active particles comprise metal nano particles and a nano protective layer formed on the surfaces of the metal nano particles, and the binder comprises at least one of a phosphate-based adhesive and a conductive silver adhesive.
2. The composite anode material of claim 1, wherein the binder is distributed between the nano-active particles and the graphite-like carbon material, and/or the binder is distributed on the surface of the graphite-like carbon material;
preferably, the phosphate-based adhesive contains phosphate;
preferably, the phosphate comprises at least one of aluminum dihydrogen phosphate, aluminum dihydrogen pyrophosphate and aluminum dihydrogen metaphosphate;
preferably, the phosphate-based adhesive further comprises alumina;
preferably, in the phosphate-based adhesive, the mass ratio of the phosphate to the alumina is (10-80): 0-10;
preferably, the median particle diameter of the nano active particles is 1nm to 500 nm;
preferably, the nano-active particles have a specific surface area of 1m2/g～500m2/g；
Preferably, the nano-active particles are distributed among the graphite-like carbon materials, and/or the nano-active particles are distributed on the surface of the graphite-like carbon materials;
preferably, the nano-active particles comprise metal nanoparticles;
preferably, the metal nanoparticles include at least one of lithium, silicon, germanium, tin, nickel, iron, cobalt, magnesium, aluminum, and copper;
preferably, the median particle diameter of the metal nanoparticles is 1nm to 300 nm;
preferably, the nano protective layer is formed in situ on the surface of the metal nano particle;
preferably, the nano protective layer includes at least one of aluminum oxide, silicon oxide, zinc oxide, titanium oxide, manganese oxide, copper oxide, cobalt oxide, silicate, phosphate, titanate, and lithium oxide;
preferably, the thickness of the nano protective layer is 1 nm-30 nm;
preferably, the graphite-based carbon material comprises at least one of artificial graphite, natural graphite and mesocarbon microbeads;
preferably, the median particle diameter of the graphitic carbon material is 1 μm to 25 μm.
3. The composite anode material according to claim 1 or 2, wherein the mass ratio of the nano active particles to the graphite-based carbon material is (0.5-5): 1;
preferably, the mass ratio of the binder to the nano active particles is (0.01-0.08): 1;
preferably, the mass content of the nano active particles is 10% to 60% based on 100% by mass of the composite anode material.
4. The composite anode material according to any one of claims 1 to 3, wherein the specific surface area of the composite anode material is 1m2/g～30m2/g；
Preferably, the powder compaction density of the composite negative electrode material is 0.5g/cm3～2g/cm3；
Preferably, the median particle diameter of the composite anode material is 1 μm to 45 μm.
5. The composite anode material according to any one of claims 1 to 4, wherein the composite anode material is of a core-shell structure, an inner core of the core-shell structure comprises the graphite-based carbon material, the nano active particles and the binder, and an outer shell of the core-shell structure is a carbon coating layer;
preferably, the thickness of the carbon coating layer is 5nm to 1000 nm.
6. The preparation method of the composite anode material is characterized by comprising the following steps of:
forming a nano protective layer on the surface of the metal nano particle to obtain nano active particles; and
mixing the nano active particles, the binder and the graphite carbon material in an organic solvent, drying and sintering to obtain the composite negative electrode material;
wherein the binder comprises at least one of a phosphate-based adhesive and a conductive silver adhesive.
7. The method of claim 6, wherein the method of forming the nano protective layer comprises at least one of an oxidation reaction method, a reduction reaction method, and a physical coating method;
preferably, the method of forming a nano protective layer includes: carrying out oxidation reaction on the surface of the metal nano-particle to form an oxide layer, wherein the oxide layer is a nano-protective layer;
preferably, the method of forming a nano protective layer includes: carrying out oxidation reaction on the surface of the metal nano-particle to form an oxide layer, and reducing the oxide layer by adopting a metal simple substance to form the nano-protection layer;
preferably, the metal simple substance comprises at least one of K, Na, Mg, Zn, Ca, Li, Rb and Ce.
8. The method of claim 6 or 7, wherein the organic solvent comprises at least one of tetrahydrofuran, amides, alcohols, and ketones;
preferably, the organic solvent comprises at least one of tetrahydrofuran, dimethylacetamide, C1-C6 alcohols, and C3-C8 ketones;
preferably, the C1-C6 alcohol includes at least one of methanol, ethanol, ethylene glycol, propanol, isopropanol, 1, 2-propanediol, 1, 3-propanediol, glycerol, n-butanol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, n-pentanol, and 2-hexanol;
preferably, the C3-C8 ketone comprises at least one of acetone, methyl ethyl ketone, methyl propyl ketone, N-methyl pyrrolidone, ethyl propyl ketone, methyl butyl ketone, ethyl N-butyl ketone, methyl amyl ketone, and methyl hexyl ketone;
preferably, the mixing further comprises: mixing nano active particles, a binder, a dispersant and a graphite carbon material in an organic solvent;
preferably, the dispersant comprises at least one of a silane coupling agent, n-octadecanoic acid, epoxy resin, lauric acid, polyacrylic acid, sodium dodecylbenzenesulfonate, n-eicosanoic acid, polyvinyl chloride and polyvinylpyrrolidone;
preferably, the mass ratio of the graphite-like carbon material, the organic solvent and the dispersant is (5-50): (50-200): (0.05-0.5);
preferably, the method of drying comprises at least one of vacuum drying, spray drying and rotary evaporation;
preferably, the method further comprises the step of forming a carbon coating layer: mixing the dried product with a coated carbon source, and sintering to obtain the composite negative electrode material;
preferably, the coated carbon source comprises at least one of epoxy resin, citric acid, sucrose, glucose, asphalt, phenolic resin, fructose, polyethylene glycol, polyvinyl alcohol and polyvinyl chloride;
preferably, the sintering temperature is 500-1500 ℃;
preferably, the sintering time is 1-12 h;
preferably, the sintering is performed under a protective atmosphere whose gas includes at least one of nitrogen, helium, neon, argon, krypton, and xenon.
9. Method according to any of claims 6-8, characterized in that it comprises the following steps:
carrying out oxidation reaction on the surface of the metal nano-particles to obtain nano active particles;
or carrying out oxidation reaction on the surface of the metal nano-particles to form an oxide layer, and reducing the oxide layer by adopting a metal monomer to obtain nano active particles;
mixing the nano active particles, a dispersing agent, a binder and a graphite carbon material in an organic solvent, and drying to obtain a precursor, wherein the binder comprises at least one of a phosphate-based adhesive and a conductive silver adhesive; and
and mixing the precursor with a coated carbon source, and sintering to obtain the composite anode material.
10. A lithium ion battery comprising the composite anode material according to any one of claims 1 to 5.
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