CN114097108A - Cathode material, preparation method thereof, electrochemical device and electronic device - Google Patents
Cathode material, preparation method thereof, electrochemical device and electronic device Download PDFInfo
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- CN114097108A CN114097108A CN202180004420.5A CN202180004420A CN114097108A CN 114097108 A CN114097108 A CN 114097108A CN 202180004420 A CN202180004420 A CN 202180004420A CN 114097108 A CN114097108 A CN 114097108A
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Images
Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The application provides a negative electrode material and a preparation method thereof, an electrochemical device and an electronic device, wherein the negative electrode material comprises a silicon-based material, and metal elements are arranged on the surfaces of silicon-based material particles; the metal element comprises at least one of Ge, Al, Zn, Sn, Sb, Bi, Fe, Mg, Ti, Cr, Mn, Co, Ni, Cu or Pb. The cathode material provided by the application can effectively improve the conductivity of the material, improve the cycle performance of the cathode material and reduce the expansion rate of a battery.
Description
Technical Field
The present disclosure relates to the field of negative electrode materials, and more particularly, to a negative electrode material, a method of preparing the same, an electrochemical device, and an electronic device.
Background
Currently, silicon-based negative electrode materials have gram capacities of 1500mAh/g to 4200mAh/g, and are considered as the next generation lithium ion negative electrode materials with the most application prospects. But the electrical conductivity (resistivity) of silicon>108Ω · cm), the electrical conductivity of the silicon material is generally increased by compounding the silicon material with a carbon material. However, when silicon-carbon composite is adopted, the oxygen content of the material is easily increased, and the negative electrode material containsThe increase of the oxygen content will directly result in a decrease of the first effect of the anode material. In addition, the silicon material has about 300% volume expansion and generates an unstable solid electrolyte interface film (SEI) in the charging and discharging processes, and the silicon negative electrode material can be pulverized and fall off a current collector in the charging and discharging processes, so that the active substance and the current collector lose electrical contact, the electrochemical performance is poor, the capacity attenuation and the cycling stability are reduced, and the further application of the silicon negative electrode material is hindered to a certain extent. The existing silicon-based negative electrode material has low conductivity, limits the charge/discharge efficiency, and has low first effect and poor cycle performance.
Disclosure of Invention
In view of this, the present application provides a negative electrode material, a method for preparing the same, an electrochemical device, and an electronic device, where the negative electrode material can effectively improve the conductivity of the material, improve the cycle performance of the negative electrode material, and reduce the expansion rate of the battery.
In a first aspect, the present application provides an anode material, comprising a silicon-based material, wherein the surface of the silicon-based material particle has a metal element; the metal element comprises at least one of Ge, Al, Zn, Sn, Sb, Bi, Fe, Mg, Ti, Cr, Mn, Co, Ni, Cu or Pb.
With reference to the first aspect, in one possible embodiment, the silicon-based material has a silicon element content n in mole percentageSiAnd the molar percentage content of the metal element is nMe，nMe/nSiThe ratio of (A) satisfies the relationship: 0.005<nMe/nSi<1.0。
With reference to the first aspect, in a possible implementation manner, the metal element is located in a region from the surface of the silicon-based material particle to d um, the radius of the silicon-based material particle is r um, and a ratio of d/r satisfies a relation: 0.01< d/r < 0.80.
With reference to the first aspect, in one possible embodiment, the silicon-based material includes at least one of elemental silicon, a silicon-carbon composite, a silicon-graphite-carbon composite, silica, and a silica-carbon composite.
With reference to the first aspect, in a possible embodiment, the metal element exists in a form including at least one of a simple metal substance embedded in a silicon-based material, a solid solution alloy of the metal element and the silicon element, a mutual solution of the metal element and the silicon element, or an amorphous alloy of the metal element and the silicon element.
In a second aspect, the present application provides a method for preparing an anode material, the method comprising the steps of:
adding silicon-based material particles into a mixed solution of water and ethanol containing metal oxide, uniformly mixing, and drying to obtain a precursor;
and carrying out heat treatment on the precursor under the protection of inert atmosphere or reducing atmosphere, so that metal elements are doped on the surface of the silicon-based material particles to obtain the cathode material.
With reference to the second aspect, in one possible embodiment, the method satisfies at least one of the following conditions (1) to (3):
(1) the heat treatment temperature is 500 ℃ to 1200 ℃;
(2) the heat preservation time of the heat treatment is 1 to 10 hours;
(3) the reducing atmosphere comprises at least one of nitrogen, argon, helium and hydrogen.
In a third aspect, the present application provides a negative electrode plate, including a negative electrode current collector and a negative electrode active material layer disposed on a surface of the negative electrode current collector, where the negative electrode active material layer includes the negative electrode material described in the first aspect or the negative electrode material prepared by the preparation method described in the second aspect.
In a fourth aspect, the present application provides an electrochemical device comprising an anode active material layer, wherein the anode active material layer comprises the anode material according to the first aspect or the anode material prepared by the preparation method according to the second aspect.
In combination with the fourth aspect, in one possible embodiment, the electrochemical device is a lithium ion battery.
In a fifth aspect, the present application provides an electronic device comprising the electrochemical device of the fourth aspect.
Compared with the prior art, the method has the following beneficial effects:
according to the cathode material provided by the application, the surface of the silicon-based material is doped with the metal element, so that the interface property of the silicon-based material can be improved, the reaction activity of the silicon-based material and an electrolyte is reduced, the formation of an SEI (solid electrolyte interphase) film is greatly reduced, the utilization rate of active lithium ions is improved, and the first effect of a battery is improved; the doped metal element can provide a high electron conductivity site in a donor phase for a silicon-based material, improve the electron conductivity of the material and reduce the impedance of the material and a battery; the metal elements and the silicon-based material particles coexist, so that a phase interface can be increased or an alloy can be formed, the lattice structure is improved, the energy barrier of the alloy formed by lithium ions and silicon is directly reduced, the kinetic rate of lithium desorption of the material is improved, and the ionic conductivity is improved.
Drawings
Fig. 1 is a schematic structural diagram of an anode material provided in an embodiment of the present application.
Detailed Description
While the following is a preferred embodiment of the embodiments of the present application, it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the embodiments of the present application, and such improvements and modifications are also considered to be within the scope of the embodiments of the present application.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive, and "one or more" means "a plurality of" is two or more.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In each instance, the list is merely a representative group and should not be construed as exhaustive.
In a first aspect, an embodiment of the present application provides an anode material, where the anode material includes a silicon-based material, and a surface of a particle of the silicon-based material has a metal element; the metal element comprises at least one of Ge, Al, Zn, Sn, Sb, Bi, Fe, Mg, Ti, Cr, Mn, Co, Ni, Cu or Pb.
According to the cathode material provided by the application, the surface of the silicon-based material is doped with the metal element, so that the interface property of the silicon-based material can be improved, the reaction activity of the silicon-based material and an electrolyte is reduced, the formation of an SEI (solid electrolyte interphase) film is greatly reduced, the utilization rate of active lithium ions is improved, and the first effect of a battery is improved; the doped metal can provide a high electron conductivity site in a body phase for silicon, improve the electron conductivity of the material and reduce the impedance of the material and a battery; the metal elements and the silicon-based material particles coexist, so that a phase interface can be increased or an alloy can be formed, the lattice structure is improved, the energy barrier of the alloy formed by lithium ions and silicon is directly reduced, the kinetic rate of lithium desorption of the material is improved, and the ionic conductivity is improved.
As an optional technical scheme of the application, the mole percentage content of the silicon element in the silicon-based material is nSiAnd the molar percentage content of the metal element is nMe，nMe/nSiThe ratio of (A) satisfies the relationship: 0.005<nMe/nSi<1.0. In particular, nMe/nSiThe value range of (b) may be specifically 0.005, 0.008, 0.01, 0.05, 0.08, 0.1, 0.14, 0.15, 0.16, 0.3, 0.5, 0.6, 0.7, or 0.8, etc., or may be other values within the above range, and is not limited herein. When n isMe/nSiToo large indicates that the silicon-based material is doped with too much metal elements and the cathode materialThe gram capacity of (a) is reduced and the production cost is increased; when n isMe/nSiAnd if the metal element doped in the silicon-based material is too small, the first effect of the cathode material and the electrochemical performance of the battery are reduced. Preferably, 0.059. ltoreq.nMe/nSi≤0.629。
As shown in fig. 1, the metal element is located in a region from the surface of the silicon-based material particle to d um, the radius of the silicon-based material particle is r um, and the ratio of d/r satisfies the relationship: 0.01< d/r < 0.80.
Optionally, the value range of d/r may be specifically 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.1, 0.15, 0.2, 0.25, 0.3, 0.5, 0.6, or 0.7, and the like, and may also be other values within the above range, which is not limited herein. When the value of d/r is too large, the doping depth of the metal element in the silicon-based material is too large, the doped metal element on the surface of the silicon-based material is relatively reduced, the expansion inhibition effect of the doped metal element on the silicon-based material is reduced, and the expansion rate of the battery is increased; when the value of d/r is too small, the doping depth of the metal elements in the silicon-based material is too small, and the first effect of the cathode material is reduced.
As an optional technical solution of the present application, the silicon-based material includes a silicon element, a metal element, an oxygen element, and a carbon element. I.e., within the silicon-based material particles, oxygen and carbon elements may also be present.
As an optional technical solution of the present application, the silicon-based material includes at least one of a simple substance of silicon, a silicon-carbon composite material, a silicon-graphite-carbon composite material, a silica, and a silica-carbon composite material.
As an optional technical solution of the present application, the existing form of the metal element includes at least one of a solid solution alloy formed by embedding a metal simple substance in a silicon-based material, a mutual solution formed by the metal element and the silicon element, or an amorphous alloy formed by the metal element and the silicon element.
As an alternative solution of the present application, the particle size range of the negative electrode material is 1um to 100um, specifically 1um, 5um, 10um, 15um, 20um, 30um, 40um, 50um, 60um, 70um, 80um, 90um, or 100um, etc., but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
In a second aspect, the present application provides a method for preparing an anode material, the method comprising the steps of:
step S10, adding silicon-based material particles into a mixed solution of water and ethanol containing metal oxide, uniformly mixing, and drying to obtain a precursor;
and step S20, carrying out heat treatment on the precursor under the protection of inert atmosphere or reducing atmosphere, so that metal elements are doped on the surface of the silicon-based material particles to obtain the negative electrode material.
In the scheme, metal elements can be doped into silicon-based material particles under the heat treatment of the metal oxide on the surface of the silicon-based material by mixing the metal oxide with the silicon-based material; therefore, the interfacial property of the silicon-based material is improved, the reactivity of the silicon-based material and the electrolyte is reduced, the formation of an SEI film is greatly reduced, the utilization rate of active lithium ions is improved, and the first effect of the battery is improved; the doped metal can provide a high electron conductivity site in a body phase for silicon, improve the electron conductivity of the material and reduce the impedance of the material and a battery; the metal elements and the silicon-based material particles coexist, so that a phase interface can be increased or an alloy can be formed, the lattice structure is improved, the energy barrier of the alloy formed by lithium ions and silicon is directly reduced, the kinetic rate of lithium desorption of the material is improved, and the ionic conductivity is improved.
As an optional technical scheme of the application, the proportional relation between the silicon-based material and the addition amount of the metal oxide MeO at least meets the following requirements: n is more than or equal to 0.005Me/nSiLess than or equal to 1.0. It is understood that the addition amount of the metal oxide may be increased appropriately during the preparation process to ensure that the doping reaction is sufficiently performed.
As an optional technical scheme of the application, the drying treatment mode can be oven drying, spray drying, vacuum drying, freeze drying and the like,
as an alternative embodiment of the present invention, the temperature of the heat treatment is 500 ℃ to 1200 ℃, specifically 500 ℃, 600 ℃, 700 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, or 1200 ℃, or the like, and may be other values within the above range.
The heat treatment may be carried out for a holding time of 1 to 10 hours, specifically 1 hour, 2 hours, 3 hours, 5 hours, 7 hours, 8 hours, 10 hours, or the like, or may be carried out for other values within the above range.
It is understood that the metal oxide deposited on the surface of the silicon-based material may be doped into the surface of the silicon-based material by high temperature heat treatment, resulting in a metal element doped silicon-based material.
As an optional technical solution of the present application, the carbon recombination treatment is performed under the protection of a reducing atmosphere, and the inert atmosphere or the reducing atmosphere may be at least one of nitrogen, argon, helium, hydrogen, and the like, for example.
In a third aspect, an embodiment of the present application provides a negative electrode tab, where the negative electrode tab includes a negative electrode current collector and a negative electrode active material layer located on the negative electrode current collector, and the negative electrode active material layer includes a negative electrode material according to the first aspect of the present application.
As an alternative embodiment of the present application, the negative active material layer includes a binder, and the binder includes polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymer, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, or the like, which is not limited herein.
As an alternative solution of the present application, the negative active material layer further includes a conductive material, and the conductive material includes natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powder, metal fiber, copper, nickel, aluminum, silver, or a polyphenylene derivative, and the like, which is not limited herein.
As an alternative solution, the negative electrode current collector includes, but is not limited to: copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, or a polymer substrate coated with a conductive metal.
In a fourth aspect, the present application further provides an electrochemical device, including a negative electrode active material layer, where the negative electrode active material layer includes the negative electrode material described in the first aspect or the negative electrode material prepared by the negative electrode material preparation method described in the second aspect.
As an optional technical solution of the present application, the electrochemical device further includes a positive electrode sheet, and the positive electrode sheet includes a positive current collector and a positive active material layer located on the positive current collector.
As an alternative embodiment of the present application, the positive electrode active material includes lithium cobaltate (LiCoO)2) At least one of lithium nickel manganese cobalt ternary material, lithium iron phosphate, lithium manganese iron phosphate and lithium manganate.
As an alternative solution, the positive active material layer further includes a binder and a conductive material. As can be appreciated, the binder improves the bonding of the positive electrode active material particles to each other, and also improves the bonding of the positive electrode active material to the current collector.
Specifically, the binder includes at least one of polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy, or nylon.
Specifically, the conductive material includes a carbon-based material, a metal-based material, a conductive polymer, and a mixture thereof. In some embodiments, the carbon-based material is selected from natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, or any combination thereof. In some embodiments, the metal-based material is selected from metal powder, metal fiber, copper, nickel, aluminum, or silver. In some embodiments, the conductive polymer is a polyphenylene derivative.
As an alternative solution, the positive electrode current collector includes, but is not limited to: aluminum foil.
As an alternative solution, the electrochemical device further includes an electrolyte including an organic solvent, a lithium salt, and an additive.
The organic solvent of the electrolyte according to the present application may be any organic solvent known in the art that can be used as a solvent of the electrolyte. The electrolyte used in the electrolyte according to the present application is not limited, and may be any electrolyte known in the art. The additive of the electrolyte according to the present application may be any additive known in the art as an additive of electrolytes.
In particular embodiments, the organic solvents include, but are not limited to: ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), propylene carbonate or ethyl propionate.
In a particular embodiment, the lithium salt includes at least one of an organic lithium salt or an inorganic lithium salt.
In particular embodiments, the lithium salt includes, but is not limited to: lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium difluorophosphate (LiPO)2F2) Lithium bis (trifluoromethanesulfonylimide) LiN (CF)3SO2)2(LiTFSI), lithium bis (fluorosulfonyl) imide Li (N (SO)2F)2) (LiFSI), lithium bis (oxalato) borate LiB (C)2O4)2(LiBOB) or lithium difluorooxalato borate LiBF2(C2O4)(LiDFOB)。
In a specific embodiment, the concentration of the lithium salt in the electrolyte may be 0.5 to 3 mol/L.
As an alternative solution, the electrochemical device of the present application includes, but is not limited to: all kinds of primary batteries, secondary batteries, fuel cells, solar cells or capacitors.
In a specific embodiment, the electrochemical device is a lithium secondary battery, wherein the lithium secondary battery includes, but is not limited to: a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
In a fifth aspect, embodiments of the present application further provide an electronic device, which includes the electrochemical device according to the fourth aspect.
As an optional technical solution of the present application, the electronic device includes, but is not limited to: a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a cellular phone, a portable facsimile machine, a portable copier, a portable printer, a headphone, a video recorder, a liquid crystal television, a portable cleaner, a portable CD player, a mini-disc, a transceiver, an electronic organizer, a calculator, a memory card, a portable recorder, a radio, a backup power supply, a motor, an automobile, a motorcycle, a power-assisted bicycle, a lighting apparatus, a toy, a game machine, a clock, an electric tool, a flashlight, a camera, a large-sized household battery or a lithium ion capacitor, and the like.
Taking a lithium ion battery as an example and describing the preparation of the lithium ion battery with reference to specific examples, those skilled in the art will understand that the preparation method described in the present application is only an example, and any other suitable preparation method is within the scope of the present application.
Preparation of negative electrode material
Dispersing a silicon-carbon material in a mixed solution of water and ethanol of tin chloride, uniformly stirring at 60 ℃, and drying the mixed solution to obtain a precursor;
and (3) placing the precursor in an inert atmosphere, and treating at the high temperature of 900 ℃ for 6h to obtain the tin-doped silicon-carbon material.
Specific parameters of examples 1 to 13, and comparative examples 1 to 6 were prepared according to the above-described method, as shown in table 1 below.
Secondly, testing the performance of the negative electrode material:
(1) and (3) performing electric deduction test:
the negative electrode materials prepared in the examples and the comparative examples, the conductive carbon black and the polymer were mixed in a mass ratio of 80: 10: 10 adding deionized water, stirring into slurry, coating into a coating with the thickness of 100um by using a scraper, drying in a vacuum drying oven for 12 hours at 85 ℃, cutting into a wafer with the diameter of 1cm by using a punching machine in a drying environment, selecting a ceglard composite membrane as an isolating membrane in a glove box, and adding electrolyte to assemble the button cell. The charging and discharging tests are carried out on the battery by using a blue electricity (LAND) series battery test, and the charging and discharging performance of the battery is tested.
(2) Qualitative doping of metal elements, doping depth of the doping elements and particle size test of the negative electrode material:
the types of the doping elements can be obtained by cutting the material particles, scanning SEM observation on the section obtained by cutting and X-ray energy spectrum analysis. And (3) carrying out SEM back scattering and EDS mapping test or FIB-TEM test and EDS mapping analysis on the cross section of the sample particle to obtain the doping depth d of the doping element and the radius r of the anode material particle.
(3) Testing the content of doped metal elements and silicon elements:
and (3) calcining the anode material particle sample in air or oxygen to remove carbon in the sample, digesting the obtained powder by using mixed acid, carrying out ICP-AES test, and calculating to obtain the mass ratio of the doped metal element and the silicon element.
TABLE 1 negative electrode Material Performance parameters
After the button cell was cycled 5 cycles in the table, the discharge was cut to a gram capacity with a voltage of 2.0V.
Preparation of lithium battery
(1) Preparation of positive pole piece
The positive electrode active material lithium cobaltate (LiCoO)2) Conductive carbon black and a binder polyvinylidene fluoride according to a weight ratio of 95: 2.5: 2.5, adding N-methyl pyrrolidone (NMP), and uniformly stirring under the action of a vacuum stirrer to obtain anode slurry; uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil; and drying the aluminum foil, then carrying out cold pressing, cutting and slitting, and drying under a vacuum condition to obtain the positive pole piece.
(2) Preparation of negative pole piece
The negative electrode material, graphite, and conductive agent (conductive carbon black, Super) of the above examples and comparative examples were mixed
) And binder PAA in a weight ratio of 70: 15: 5: 10, mixing, adding deionized water, controlling the solid content to be about 5 wt% to 70 wt%, obtaining negative electrode slurry under the action of a vacuum stirrer, and adjusting the viscosity of the slurry to be about 4000 pas to 6000 pas; uniformly coating the negative electrode slurry on a copper foil of a negative electrode current collector; and drying the copper foil, and then drying the copper foil under a vacuum condition after cold pressing, cutting and slitting to obtain the negative pole piece.
(3) Electrolyte solution
In a dry argon atmosphere glove box, LiPF6 was added to a solvent in which Propylene Carbonate (PC), Ethylene Carbonate (EC), and diethyl carbonate (DEC) were mixed in a weight ratio of about 1: 1: 1, and the mixture was uniformly mixed, wherein the concentration of LiPF6 was about 1.15mol/L, and about 12.5 wt% of fluoroethylene carbonate (FEC) was added thereto, and the mixture was uniformly mixed to obtain an electrolyte.
(3) Isolation film
The polyethylene porous polymer film is used as a separation film.
(4) Preparation of lithium ion battery
Stacking the positive pole piece, the isolating film and the negative pole piece in sequence to enable the isolating film to be positioned between the positive pole piece and the negative pole piece to play an isolating role, and then winding to obtain a bare cell; and (3) after welding the lug, placing the bare cell in an outer packaging foil aluminum-plastic film, injecting the prepared electrolyte into the dried bare cell, and performing vacuum packaging, standing, formation, shaping, capacity test and other procedures to obtain the lithium ion battery.
And fourthly, testing the performance of the lithium battery:
(1) lithium ion battery cycle performance test
And (3) placing the lithium ion battery in a constant temperature box with the temperature of 45 ℃ (25 ℃), and standing for 30 minutes to keep the temperature of the lithium ion battery constant. And charging the lithium ion battery reaching the constant temperature to the voltage of 4.4V at a constant current of 0.7C, then charging the lithium ion battery to the current of 0.025C at a constant voltage of 4.4V, standing for 5 minutes, discharging the lithium ion battery to the voltage of 3.0V at a constant current of 0.5C, taking the capacity obtained in the step as the initial capacity, performing a cyclic test on the charge of 0.7C/discharge of 0.5C, and taking the ratio of the capacity of each step to the initial capacity to obtain a capacity fading curve. The cycle number of the battery with the capacity retention rate of 90% after the cycle at 25 ℃ is recorded as the room-temperature cycle performance of the battery, the cycle number of the battery with the capacity retention rate of 80% after the cycle at 45 ℃ is recorded as the high-temperature cycle performance of the battery, and the cycle performance of the materials is compared by comparing the cycle number of the two cases.
(2) And (3) testing discharge rate:
and (3) placing the lithium ion battery in a constant temperature box at 25 ℃, and standing for 30 minutes to keep the temperature of the lithium ion battery constant. Discharging the lithium ion battery reaching the constant temperature at a constant current of 0.2C until the voltage is 3.0V, standing for 5min, charging at a constant current of 0.5C until the voltage is 4.45V, then charging at a constant voltage of 4.45V until the current is 0.05C, standing for 5min, adjusting the discharge rate, performing discharge tests at 0.2C, 0.5C, 1C, 1.5C and 2.0C respectively to obtain discharge capacities respectively, comparing the capacity obtained at each rate with the capacity obtained at 0.2C, and comparing the rate performance by comparing the ratio of 2C to 0.2C.
(3) And (3) testing the charging rate:
and (3) placing the lithium ion battery in a constant temperature box at 25 ℃, and standing for 30 minutes to keep the temperature of the lithium ion battery constant. Charging the lithium ion battery reaching the constant temperature to 4.45V at 0.2C, charging at constant voltage to 0.05C, standing for 5min, discharging at 0.5C to 3.0V, standing for 5min, adjusting the charging multiplying power, performing charging tests at 0.2C, 0.5C, 1C, 1.5C and 2.0C respectively to obtain the charging capacity respectively, comparing the capacity obtained at each multiplying power with the capacity obtained at 0.2C, and comparing the multiplying power performance by comparing the ratio of 2C to 0.2C.
(4) And (3) testing the full charge expansion rate of the battery:
and (3) testing the thickness of the fresh battery in the half-charging (50% charging State (SOC)) by using a spiral micrometer, circulating to 400 circles, and testing the thickness of the battery at the moment by using the spiral micrometer when the battery is in the full-charging (100% SOC) state, and comparing the thickness of the battery with the thickness of the fresh battery in the initial half-charging (50% SOC) state to obtain the expansion rate of the full-charging (100% SOC) battery at the moment.
The performance parameters of the negative electrode materials of examples 1 to 13 and the negative electrode materials of comparative examples 1 to 6 manufactured according to the above-described methods are shown in table 1, and the performance test results of the lithium batteries manufactured therefrom are shown in table 2.
TABLE 2
From the test results of examples 1 to 4 and comparative examples 1 and 2, it can be seen that, in comparative examples 1 and 2, no metal element is doped, and after the metal element is doped in the silicon-based materials of different types in examples 1 to 4, the first effect of the silicon-based materials is improved, and the first effect and the charging/discharging efficiency of the battery made of the materials are improved. According to the test results of the embodiments 1 to 4, under the condition that the doping depth and the doping amount are similar, the first efficiency of the silicon oxide material is lower and the gram capacity of the silicon oxide material is lower due to lower electronic conductivity, more side reactions and high oxygen content of the silicon oxide material, so that the first efficiency of the battery is lower; since the electronic conductivity of the silicon monoxide is lower than that of other materials, the charge/discharge efficiency is also lower; but the volume change caused by lithium intercalation and deintercalation is smaller, so that the capacity retention rate and the cell expansion rate are better.
According to the test results of the embodiment 4 and the comparative example 2, the Ge-doped silicon material can improve the lattice structure, increase the kinetics of lithium intercalation and deintercalation of the material, obviously improve the first effect of the material, and further improve the electrochemical performance of the battery. The silicon-carbon composite materials in the examples 2 and 3 have carbon components to enhance the electronic conductivity of the silicon-carbon composite materials, so that the first efficiency of the examples 2 and 3 is higher than that of the examples 1 and 4 and the comparative examples 1 and 2, and further the first efficiency and the charge/discharge efficiency of the battery are higher; meanwhile, due to the existence of the carbon component, the capacity retention rate of the battery is improved, and the expansion rate of the battery is reduced.
The elemental silicon powder and the silicon monoxide powder in comparative examples 1 and 2 are not doped with the metal element Ge, and although the gram capacity of the material is not affected, the first effect is lower than that in examples 1 and 4, and the material does not have a protective interface of a carbon material, so that more SEIs are easily generated, and the electrochemical performance parameters such as the first effect, the charge/discharge rate, the capacity retention rate, the cell expansion rate and the like of the battery are deteriorated.
A comparison of the test data according to examples 5 to 7 illustrates the effect of different doping elements on the material and cell properties. In example 5, Si and Sn cannot form a solid solution, so that the Sn element exists as Sn metal simple substance particles in a doped form on the surface of the silicon-based material, and the Sn metal simple substance can be used as a bulk phase conductive agent of the silicon-based material to increase the electronic conductivity of the silicon-based material, thereby improving the charge/discharge efficiency of the battery. In example 6, Si and Al can form two solid solutions, so that the doping form of Al on the surface of the silicon-based material exists in the form of two solid solutions, which not only can be used as a bulk conductive agent to improve the electronic conductivity of the silicon material, but also can improve the existing form of part of Si element, increase the deintercalation rate of lithium ions in the solid solutions, and improve the dynamic performance of the material. In example 7, Si and Cu have 5 or more eutectic morphologies and a plurality of solid solutions, and since Cu has high electronic conductivity, the conductivity of the material can be increased more than that of Si and Al alloy. In addition, although the Cu element can not provide capacity for lithium intercalation, the gram capacity of the material is low, the doped metal element Cu can stabilize the interface of the material, reduce the formation of SEI (solid electrolyte interphase), and improve the first effect of the silicon-based negative electrode material. Therefore, the negative electrode material of example 7 is best in all properties among examples 5 to 7.
The comparison of the test data according to examples 1, 8 to 10 and comparative examples 3, 4 illustrates the effect of metal doping depth on the electrochemical performance of the material and cell. Under the condition that the doped metal elements are the same and the doping amount is similar, the gram capacity of the cathode material is similar; with the increase of the doping depth of the metal element, the doping metal element on the surface of the silicon-based material is reduced, the first effect of the material is reduced, and further the first effect of the battery is reduced. While the element is doped on the outermost surface in the comparative example 2, the improvement on the performance of the material and the battery is limited. In comparative example 3, the element doping penetrates almost the entire interior of the particles of the base material, and the surface doping metal element is less, so that the first efficiency of the negative electrode material and the battery of comparative example 3 is lower, but the charge/discharge rate of the battery is higher, compared to example 1. And because the doping distribution of the metal elements is uniform, the surface layer has a limited effect on limiting the internal volume expansion, and the expansion rate of the battery is improved.
The comparison of the test data according to examples 1, 11 to 13 and comparative examples 1, 5 and 6 illustrates the effect of the doping amount of the metal element on the electrochemical performance of the anode material and the battery. According to examples 11 to 13, it can be seen that in the case where the doping depths of the metal elements are close, the gram capacity of the anode material decreases as the doping amount of the metal element increases, because the gram capacity of silicon is higher than that of the doped metal element; but the first effect of the negative electrode material and the electrochemical performance of the battery are improved along with the increase of the doping amount. Comparative example 5 illustrates that when the doping amount of the metal element is too small, the performance of the anode material and the battery is only slightly improved compared with comparative example 1. Comparative example 6 illustrates that the doping amount of the metal element is too high, the gram capacity of the material is reduced, and the improvement effect on the electrochemical performance of the material and the battery is also reduced; and the cost of the doping element is larger than that of the silicon element, which is not beneficial to practical application and production cost reduction.
Although the present application has been described with reference to preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the application.
Claims (11)
1. The negative electrode material is characterized by comprising a silicon-based material, wherein the surface of silicon-based material particles is provided with a metal element; the metal element comprises at least one of Ge, Al, Zn, Sn, Sb, Bi, Fe, Mg, Ti, Cr, Mn, Co, Ni, Cu or Pb.
2. The negative electrode material as claimed in claim 1, wherein the silicon-based material contains silicon element in a molar percentage of nSiAnd the molar percentage content of the metal element is nMe，nMe/nSiThe ratio of (A) satisfies the relationship: 0.005<nMe/nSi<1.0。
3. The negative electrode material of claim 1, wherein the metal element is located in a region from the surface of the silicon-based material particle to d um, the radius of the silicon-based material particle is r um, and the ratio of d/r satisfies the relationship: 0.01< d/r < 0.80.
4. The anode material of claim 1, wherein the silicon-based material comprises at least one of elemental silicon, a silicon-carbon composite, a silicon-graphite-carbon composite, silica, and a silica-carbon composite.
5. The anode material according to claim 1, wherein the metal element is present in a form including at least one of a simple metal substance embedded in a silicon-based material, a solid solution alloy of the metal element and silicon element, a mutual solution of the metal element and silicon element, or an amorphous alloy of the metal element and silicon element.
6. A method for preparing the negative electrode material according to any one of claims 1 to 5, characterized by comprising the steps of:
adding silicon-based material particles into a mixed solution of water and ethanol containing metal oxide, uniformly mixing, and drying to obtain a precursor;
and carrying out heat treatment on the precursor under the protection of inert atmosphere or reducing atmosphere, so that metal elements are doped into the surface of the silicon-based material, and obtaining the cathode material.
7. The production method according to claim 6, characterized in that the method satisfies at least one of the following conditions (1) to (3):
(1) the heat treatment temperature is 500 ℃ to 1200 ℃;
(2) the heat preservation time of the heat treatment is 1 to 10 hours;
(3) the reducing atmosphere comprises at least one of nitrogen, argon, helium and hydrogen.
8. A negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer arranged on the surface of the negative electrode current collector, wherein the negative electrode active material layer comprises the negative electrode material in any one of claims 1 to 5 or the negative electrode material prepared by the preparation method in any one of claims 6 to 7.
9. An electrochemical device comprising a negative electrode active material layer, characterized in that the negative electrode active material layer comprises the negative electrode material according to any one of claims 1 to 5 or the negative electrode material produced by the production method according to any one of claims 6 to 7.
10. The electrochemical device of claim 9, wherein the electrochemical device is a lithium ion battery.
11. An electronic device, characterized in that the electronic device comprises the electrochemical device according to claim 10.
Applications Claiming Priority (1)
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