CN108807956A - A kind of lithium ion battery nucleocapsid negative material and preparation method thereof - Google Patents
A kind of lithium ion battery nucleocapsid negative material and preparation method thereof Download PDFInfo
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- CN108807956A CN108807956A CN201811004804.3A CN201811004804A CN108807956A CN 108807956 A CN108807956 A CN 108807956A CN 201811004804 A CN201811004804 A CN 201811004804A CN 108807956 A CN108807956 A CN 108807956A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
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- 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 kind of lithium ion battery nucleocapsid negative materials.When prepared by the negative material, nano-silicon is deposited in nanoscale lithium titanate particle by lithium titanate powder ball milling at nanoscale lithium titanate particle first, obtains negative material presoma one；Prepare stannic oxide/graphene nano piece suspension；Negative material presoma one is added in stannic oxide/graphene nano piece suspension, atomization drying is carried out after high speed dispersion, obtains negative material presoma two；Negative material presoma two and organic cracking carbon source are carried out homogeneous compound, then high temperature sintering obtains the negative material of nucleocapsid.The kernel of negative material of the present invention is nano-silicon, nano lithium titanate and stannic oxide/graphene nano piece, and the lithium titanate particle for being attached with nano-silicon is evenly distributed between stannic oxide/graphene nano piece, and shell is organic cracking carbon-coating；With high power capacity, high magnification, low bulk and excellent cycle performance, and preparation process is simple, green non-pollution, is suitble to large-scale production.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of lithium ion battery nucleocapsid negative materials
And preparation method thereof.
Background technology
Under current environmental pollution, the background of energy shortages, what lithium ion battery because of its cleanliness without any pollution, was efficiently recycled
Speciality, be the main electrical source of power of current new-energy automobile.Electrode material in lithium ion battery has decision to battery performance
The influence of property, wherein negative material play a crucial role the raising of performance of lithium ion battery.
Silicon have superelevation theoretical specific capacity (4200mAh/g) and lower de- lithium current potential (<0.5V), and the voltage of silicon is flat
Platform is slightly above stannic oxide/graphene nano piece, and in charging, difficulty causes surface to analyse lithium, and security performance is more preferable.However, silicon is in charge and discharge
The volume change of Shi Gaoda 300%, makes that it bears prodigious mechanicals efforts in charge and discharge cycles and gradual dusting is caved in, with
Collector loses electrical contact, eventually leads to battery failure, shows very poor cycle performance.Lithium titanate is a kind of " zero strain " material
Material, deintercalation of the lithium ion in lithium titanate be reversible, and lithium ion is in embedded or during deviate from lithium titanate, crystal form
It does not change, volume change is less than 1%, to make it have excellent cycle performance and stable discharge voltage.But metatitanic acid
Lithium material theoretical specific capacity only 175mAh/g, specific capacity in actual use is lower, and platform voltage height etc..
Invention content
In order to solve the problems, such as above-mentioned silicon and lithium titanate as electrode material, the present invention provides a kind of lithium ion battery core
Shell structure negative material and preparation method thereof, lithium ion battery of the present invention nucleocapsid negative material, by nano-silicon, receives
The advantage of rice lithium titanate and stannic oxide/graphene nano piece be combined with each other, and nano-silicon promotes whole specific capacity, and with the side of CVD deposition
Formula is attached to the surface of nano lithium titanate, and nano lithium titanate bears and buffer the volume of nano-silicon both as the carrier of nano-silicon
Expansion, moreover it is possible to promote the ion transfer rate of negative material；Preparation process is simple, green non-pollution, is suitble to large-scale production.
In order to achieve the above purpose, technical scheme is as follows：
Present invention aims at provide a kind of lithium ion battery nucleocapsid negative material, it is characterised in that：It is described negative
Pole material is nucleocapsid, and kernel is nano-silicon, nano lithium titanate and stannic oxide/graphene nano piece, and wherein nano-silicon is attached to titanium
The surface of sour lithium particle, the lithium titanate particle for being attached with nano-silicon are evenly distributed between stannic oxide/graphene nano piece, and shell is
Organic cracking carbon-coating；The median particle diameter of the nano-silicon is 5~100nm；The median particle diameter of the nano lithium titanate be 1~
500nm；The thickness of the stannic oxide/graphene nano piece is 1~100nm；The thickness of organic cleaving layer is 0.1~5 μm.
Further, in the negative material：The content of nano-silicon is 5wt%~40wt%, and the content of lithium titanate is
The content of 5wt%~40wt%, stannic oxide/graphene nano piece are 1wt%~20wt%, and the content of organic cracking carbon-coating is
10wt%~60wt%；The median particle diameter of the negative material is 1~30 μm；The specific surface area of the negative material be 1~
30m2/g；The powder body compacted density of the negative material is 0.1~2.5g/cm3, preferably 0.5~2g/cm3。
Another object of the present invention is to provide a kind of lithium ion battery preparation method of nucleocapsid negative material, packets
Include following steps：
(1) lithium titanate powder is placed in ball milling in ball mill, nanoscale lithium titanate particle is made；
(2) CVD deposition method is utilized, nano-silicon is deposited in nanoscale lithium titanate particle made from step (1), is born
Pole material precursor one；
(3) stannic oxide/graphene nano piece suspension is prepared；
(4) negative material presoma one made from step (2) is added to stannic oxide/graphene nano piece made from step (3)
In suspension, composite mortar is obtained after high speed dispersion, then carry out atomization drying, obtain negative material presoma two；
(5) negative material presoma two made from step (4) is homogeneous compound with the progress of organic cracking carbon source, it is subsequently placed in
In reactor, high temperature sintering obtains the negative material of nucleocapsid under atmosphere of inert gases.
Preferably, in the step (1)：The median particle diameter of the lithium titanate powder is 1~50 μm, purity >=
99.9%；The one kind of the ball mill in high-speed stirred mill, planetary ball mill, tube mill and sand mill, preferably sand
Grinding machine；The material of ball milling pearl in the ball-grinding machine is in stainless steel, agate, ceramics, zirconium oxide and hard alloy
One kind, a diameter of 1~10mm of the ball milling pearl；In mechanical milling process, ratio of grinding media to material is (10~200):1, rotational speed of ball-mill be 50~
2000rpm, Ball-milling Time are 1~50h；The median particle diameter of the nanoscale lithium titanate particle is 1~500nm.
Preferably, the step (2) is specially：The nano lithium titanate particle obtained in step (1) is added in CVD stoves
In courage, it is passed through inert gas and excludes CVD furnace airs, until oxygen content≤300ppm, then with the heating of 1.0~5 DEG C/min
Speed, is warming up to 400~1000 DEG C, after 1~8h of roasting time, then is continually fed into organic silicon source gas and carries out chemical vapor deposition
Product, 0.5~5h of chemical vapor deposition time, organic silicon source gas flow are 1~10L/min, and then 1~5h of Isothermal sinter, makes
Silicon nanoparticle is uniformly deposited in nanoscale lithium titanate particle, obtains negative material presoma one；Wherein, described organic
Silicon source gas is silane, dichlorosilane, trichlorosilane, silicon tetrachloride, the combination of one or more of ocratation；
The inert gas is at least one of nitrogen, helium, neon and argon gas.
Preferably, the step (3) is specially：Under conditions of ice-water bath, graphite is added to the concentrated sulfuric acid and concentrated nitric acid
Mixed liquor in, stir evenly, potassium permanganate be then added, be warming up to 50~200 DEG C, be stirred to react 1~20h, make graphite quilt
Complete oxidation generates graphite oxide, then hydrogen peroxide is added in graphite oxide solution until there is no gases to generate, and removing is not
The potassium permanganate of reaction is used in combination deionized water to clean 1~10 time, the solution after cleaning is finally carried out ultrasonic stripping, oxygen is made
Graphite alkene nanometer sheet suspension；Wherein, the concentrated sulfuric acid and the volume ratio of concentrated nitric acid mixing are 1 in mixed liquor:1；Every gram of stone
Ink is in requisition for 10~40mL mixed liquors；The mass ratio of the graphite and potassium permanganate is 1:(1~5)；The graphene oxide
The thickness of nanometer sheet is 1~100nm.
Preferably, the step (4) is specially：Negative material presoma one made from step (2) is added to step (3)
In stannic oxide/graphene nano piece suspension obtained, imported in high speed dispersor after being slowly stirred 0.5~5h, and be passed through indifferent gas
Body, rotating speed are 1000~12000rpm, and 1~10h of high speed dispersion time obtains finely dispersed composite mortar, then will be compound
Slurry carries out atomization drying, obtains negative material presoma two；Wherein, the solid content of the compound slurry is 10~70wt%；
The high speed dispersor is one kind in planetary ball mill, tube mill, type taper grinder, rod mill, homogenizer and sand mill；Institute
It is at least one of nitrogen, helium, neon and argon gas to state inert gas；The hot-air inlets temperature of the atomization drying is
180~350 DEG C, outlet temperature is 110~200 DEG C.
Preferably, in the step (5)：The negative material presoma two is mixed with organic cracking carbon source, mixes matter
Amount is than being 1:(0.1~5) is subsequently placed in VC mixing machines, adjusts 5~100Hz of frequency, mixes at least 20min, is subsequently placed in anti-
It answers in device, is passed through inert gas, be warming up to 400~1000 DEG C, heat preservation 0.5~8h postcoolings obtain nucleocapsid to room temperature
Negative material；Wherein, organic cracking carbon source is in pitch, epoxy resin, phenolic resin, furfural resin and acrylic resin
At least one, the grain size of organic cracking carbon source is 1~20 μm；The inert gas is nitrogen, helium, neon and argon gas
At least one of；The reactor is one kind in vacuum drying oven, batch-type furnace, rotary furnace, roller kilns, pushed bat kiln and tube furnace
The beneficial effects of the invention are as follows：Lithium ion battery of the present invention nucleocapsid negative material, by nano-silicon, receives
The advantage of rice lithium titanate and stannic oxide/graphene nano piece be combined with each other, and nano-silicon promotes whole specific capacity, and with the side of CVD deposition
Formula is attached to the surface of nano lithium titanate, and nano lithium titanate bears and buffer the volume of nano-silicon both as the carrier of nano-silicon
Expansion, moreover it is possible to promote the ion transfer rate of negative material.Graphene oxide has superior electric conductivity, the specific surface area of superelevation
It with good mechanical strength, is evenly distributed on inside negative material with nanometer sheet form, the electricity of the multiplication entirety of the energy order of magnitude
Conductance, while its lamellar structure for being formed inside negative material, can greatly fetter bulk expansion, the frame knot of stabilizing material
Structure.Organic cracking carbon-coating can be effectively isolated electrolyte and protect kernel, inner nuclear material is avoided to be electrolysed as shell clad
The etch of liquid；Lithium ion battery of the present invention has high power capacity, high magnification, low bulk and excellent with nucleocapsid negative material
Cycle performance, and preparation process is simple, green non-pollution, is suitble to large-scale production.
Description of the drawings
Fig. 1 is the nucleocapsid schematic diagram of lithium ion battery nucleocapsid negative material of the present invention.
In figure：The organic cracking carbon-coatings of 1-；2- stannic oxide/graphene nano pieces；3- lithium titanates；4- nano-silicons.
Specific implementation mode
Firstly, it is necessary to which explanation, will illustrate lithium ion battery core of the present invention by way of example below
The characteristics of shell structure negative material and preparation method thereof and advantage etc., however what all descriptions were intended merely to illustrate, and
It should not be construed as forming any restrictions to the present invention.
Below just by the embodiment that provides come to lithium ion battery nucleocapsid negative material of the present invention and its
Preparation method illustrates.
Embodiment 1
The preparation method of the nucleocapsid negative material of lithium ion battery described in the present embodiment, according to the following steps specifically into
Row:
(1) it is that 30 μm of lithium titanate powders are placed in ball milling in planetary ball mill by median particle diameter, the material of ball milling pearl is oxygen
Change zirconium, a diameter of 6mm of ball milling pearl, ratio of grinding media to material 8:1, rotational speed of ball-mill 800rpm, Ball-milling Time 20h obtain median particle diameter
For the lithium titanate particle of 400nm；
(2) the nano lithium titanate particle obtained in step (1) is added in CVD furnace internal-linings, is passed through nitrogen and excludes CVD stoves
Interior air then with the heating rate of 2 DEG C/min, is warming up to 900 DEG C until oxygen content≤300ppm, after roasting time 2h, then
It is continually fed into trichlorosilane gas and carries out chemical vapor deposition, chemical vapor deposition time 1h, trichlorosilane gas flow is 3L/
Min, then Isothermal sinter 2h, makes silicon nanoparticle uniformly be deposited on nano lithium titanate particle, obtains negative material forerunner
Body one；
(3) under conditions of ice-water bath, 5g graphite is added in the mixed liquor of the 40mL concentrated sulfuric acids and 40mL concentrated nitric acids, is stirred
It mixes uniformly, 10g potassium permanganate is then added, is warming up to 80 DEG C, is stirred to react 5h, graphite is made to be fully oxidized, generate oxidation stone
Ink, then hydrogen peroxide is added in graphite oxide solution until there is no gases to generate, unreacted potassium permanganate is removed, is used in combination
Deionized water is cleaned 5 times, and the solution after cleaning is finally carried out ultrasonic stripping, stannic oxide/graphene nano piece suspension is made；Oxygen
The thickness of graphite alkene nanometer sheet is 90nm；
(4) negative material presoma one made from step (2) is added to stannic oxide/graphene nano piece made from step (3)
In suspension, negative material presoma one and the mass ratio of stannic oxide/graphene nano piece are 1：1, compound slurry, it is slowly stirred
It is imported in high speed dispersor after 2h, and is passed through nitrogen and is protected, rotating speed 3000rpm, jitter time 2h, obtaining solid content is
Then composite mortar is carried out atomization drying by the composite mortar of 60wt%, the hot-air inlets temperature of spray drying is 180 DEG C,
Outlet temperature is 120 DEG C and obtains negative material presoma two；
(5) the negative material presoma two is mixed with the phenolic resin that grain size is 3 μm, mixing quality ratio is 1:1, so
It is placed in VC mixing machines, adjusts frequency 50Hz, mix 30min, be subsequently placed in reactor, be passed through inert gas, be warming up to
900 DEG C, heat preservation 5h postcoolings obtain nucleocapsid negative material to room temperature.
Lithium ion battery manufactured in the present embodiment is in nucleocapsid negative material：The median particle diameter of nano-silicon 4 is 80nm；
The median particle diameter of lithium titanate 3 is 400nm；The thickness of stannic oxide/graphene nano piece 2 is 90nm；The thickness of organic cleaving layer 1 is 5 μ
m；In negative material：The content of nano-silicon 4 is 15wt%, and the content of lithium titanate 3 is 10wt%, stannic oxide/graphene nano piece 2
Content is 25wt%, and the content of organic cracking carbon-coating 1 is 50wt%；The median particle diameter of negative material is 20 μm；Negative material
Specific surface area is 2.2m2/g；The powder body compacted density of negative material is 1.38g/cm3。
Embodiment 2
The preparation method of the nucleocapsid negative material of lithium ion battery described in the present embodiment, according to the following steps specifically into
Row:
(1) it is that 15 μm of lithium titanate powders are placed in ball milling in planetary ball mill by median particle diameter, the material of ball milling pearl is oxygen
Change zirconium, a diameter of 8mm of ball milling pearl, ratio of grinding media to material 50:1, rotational speed of ball-mill 1200rpm, Ball-milling Time 30h obtain intermediate value grain
Diameter is the lithium titanate particle of 300nm；
(2) the nano lithium titanate particle obtained in step (1) is added in CVD furnace internal-linings, is passed through nitrogen and excludes CVD stoves
Interior air then with the heating rate of 2 DEG C/min, is warming up to 800 DEG C until oxygen content≤300ppm, after roasting time 2h, then
It is continually fed into trichlorosilane gas and carries out chemical vapor deposition, chemical vapor deposition time 2h, trichlorosilane gas flow is 3L/
Min, then Isothermal sinter 2h, makes silicon nanoparticle uniformly be deposited on nano lithium titanate particle, obtains negative material forerunner
Body one；
(3) under conditions of ice-water bath, 5g graphite is added in the mixed liquor of the 80mL concentrated sulfuric acids and 80mL concentrated nitric acids, is stirred
It mixes uniformly, 10g potassium permanganate is then added, is warming up to 100 DEG C, is stirred to react 8h, graphite is made to be fully oxidized, generate oxidation stone
Ink, then hydrogen peroxide is added in graphite oxide solution until there is no gases to generate, unreacted potassium permanganate is removed, is used in combination
Deionized water is cleaned 5 times, and the solution after cleaning is finally carried out ultrasonic stripping, stannic oxide/graphene nano piece suspension is made；Oxygen
The thickness of graphite alkene nanometer sheet is 50nm；
(4) negative material presoma one made from step (2) is added to stannic oxide/graphene nano piece made from step (3)
In suspension, negative material presoma one and the mass ratio of stannic oxide/graphene nano piece are 2：1, import high speed after being slowly stirred 2h
It in dispersion machine, and is passed through nitrogen and is protected, rotating speed 6000rpm, jitter time 5h, it is the compound of 40wt% to obtain solid content
Slurry.Then composite mortar is subjected to atomization drying, the hot-air inlets temperature of spray drying is 220 DEG C, outlet temperature 140
DEG C obtain negative material presoma two.
(5) the negative material presoma two is mixed with the hard pitch that grain size is 3 μm, mixing quality ratio is 3:1, so
It is placed in VC mixing machines, adjusts frequency 50Hz, mix 30min, be subsequently placed in reactor, be passed through inert gas, be warming up to
800 DEG C, heat preservation 5h postcoolings obtain nucleocapsid negative material to room temperature.
Lithium ion battery manufactured in the present embodiment is in nucleocapsid negative material：The median particle diameter of nano-silicon 4 is 80nm；
The median particle diameter of lithium titanate 3 is 400nm；The thickness of stannic oxide/graphene nano piece 2 is 50nm；The thickness of organic cleaving layer 1 is 4 μ
m；In negative material：The content of nano-silicon 4 is 20wt%, and the content of lithium titanate 3 is 30wt%, stannic oxide/graphene nano piece 2
Content is 25wt%, and the content of organic cracking carbon-coating 1 is 25wt%；The median particle diameter of negative material is 16 μm；Negative material
Specific surface area is 2.5m2/g；The powder body compacted density of negative material is 1.33g/cm3。
Embodiment 3
The preparation method of the nucleocapsid negative material of lithium ion battery described in the present embodiment, according to the following steps specifically into
Row:
(1) it is that 5 μm of lithium titanate powders are placed in ball milling in planetary ball mill by median particle diameter, the material of ball milling pearl is oxidation
Zirconium, a diameter of 4mm of ball milling pearl, ratio of grinding media to material 8:1, rotational speed of ball-mill 2000rpm, Ball-milling Time 40h, obtaining median particle diameter is
The lithium titanate particle of 200nm；
(2) the nano lithium titanate particle obtained in step (1) is added in CVD furnace internal-linings, is passed through nitrogen and excludes CVD stoves
Interior air then with the heating rate of 2 DEG C/min, is warming up to 700 DEG C until oxygen content≤300ppm, after roasting time 2h, then
It is continually fed into trichlorosilane gas and carries out chemical vapor deposition, chemical vapor deposition time 4h, trichlorosilane gas flow is 3L/
Min, then Isothermal sinter 2h, makes silicon nanoparticle uniformly be deposited on nano lithium titanate particle, obtains negative material forerunner
Body one；
(3) under conditions of ice-water bath, 5g graphite is added in the mixed liquor of the 80mL concentrated sulfuric acids and 80mL concentrated nitric acids, is stirred
It mixes uniformly, 10g potassium permanganate is then added, is warming up to 160 DEG C, is stirred to react 10h, graphite is made to be fully oxidized, generate oxidation
Graphite, then hydrogen peroxide is added in graphite oxide solution until there is no gases to generate, unreacted potassium permanganate is removed, and
It is cleaned 5 times with deionized water, the solution after cleaning is finally subjected to ultrasonic stripping, stannic oxide/graphene nano piece suspension is made；
The thickness of stannic oxide/graphene nano piece is 30nm；
(4) negative material presoma one made from step (2) is added to stannic oxide/graphene nano piece made from step (3)
In suspension, negative material presoma one and the mass ratio of stannic oxide/graphene nano piece are 4：1, import high speed after being slowly stirred 2h
It in dispersion machine, and is passed through nitrogen and is protected, rotating speed 9000rpm, jitter time 8h, it is the compound of 20wt% to obtain solid content
Slurry.Then composite mortar is subjected to atomization drying, the hot-air inlets temperature of spray drying is 280 DEG C, outlet temperature 150
DEG C obtain negative material presoma two.
(5) the negative material presoma two is mixed with the furfural resin that grain size is 3 μm, mixing quality ratio is 2:1, so
It is placed in VC mixing machines, adjusts frequency 50Hz, mix 30min, be subsequently placed in reactor, be passed through inert gas, be warming up to
700 DEG C, heat preservation 5h postcoolings obtain nucleocapsid negative material to room temperature.
Lithium ion battery manufactured in the present embodiment is in nucleocapsid negative material：The median particle diameter of nano-silicon 4 is 80nm；
The median particle diameter of lithium titanate 3 is 400nm；The thickness of stannic oxide/graphene nano piece 2 is 30nm；The thickness of organic cleaving layer 1 is 3 μ
m；In negative material：The content of nano-silicon 4 is 25wt%, and the content of lithium titanate 3 is 28.3wt%, stannic oxide/graphene nano piece 2
Content be 13.4wt%, the content of organic cracking carbon-coating 1 is 33.3wt%；The median particle diameter of negative material is 20 μm；Cathode
The specific surface area of material is 2.8m2/g；The powder body compacted density of negative material is 1.29g/cm3。
Comparative example 1
The preparation method of the nucleocapsid negative material of lithium ion battery described in the present embodiment and embodiment 1 difference lies in
Without step (1) and (2), i.e., lithium titanate is free of in negative material, remaining will not be described in great detail here with embodiment 1.
Comparative example 2
The preparation method of the nucleocapsid negative material of lithium ion battery described in the present embodiment and embodiment 1 difference lies in
Without step (3), i.e., nano-silicon is free of in negative material, remaining will not be described in great detail here with embodiment 1.
Comparative example 3
The preparation method of the nucleocapsid negative material of lithium ion battery described in the present embodiment and embodiment 1 difference lies in
Without step (4), i.e., stannic oxide/graphene nano piece is free of in negative material, remaining will not be described in great detail here with embodiment 1.
Lithium ion battery is prepared with the negative material of Examples 1 to 3 and comparative example 1~3 and is detected, and steps are as follows：It will bear
Pole material, conductive agent and binder in mass ratio 93:2:In a solvent, control solid content is coated on copper to 5 mixed dissolutions 45%
On foil collector, cathode pole piece is made in vacuum drying；Then tertiary cathode pole piece, the 1mol/L prepared by traditional maturation process
LiPF6/EC+DMC+EMC (v/v=1:1:1) electrolyte, Celgard2400 diaphragms, shell are assembled using conventional production process
18650 cylinder single batteries；On Wuhan Jin Nuo Electronics Co., Ltd.s LAND battery test systems, filling for the battery of preparation is tested
Discharge performance, test condition are：Room temperature, 0.2C constant current charge-discharges, charging/discharging voltage are limited in 3.2V~4.3V；Test result is such as
Shown in table 1.
The negative material of 1 Examples 1 to 3 of table and comparative example 1~3 prepares cell testing results
By table 1 as it can be seen that the nucleocapsid negative material prepared using herein described method, passes through adjusting nano-silicon, titanium
The ratio of sour lithium and graphene adjusts the comprehensive performance of negative material, the low (1~5m of specific surface area2/ g), compacted density is high
(1.3~1.5g/cm3), discharge capacity can be more than 1100mAh/g, and initial coulomb efficiency can be more than 91%, 10C capacity retention ratios
85% can be more than, 300 weeks capacity retention ratios of cycle are up to 90% or more.Comparative example 1 is added without lithium titanate, obtained negative material
Discharge capacity it is higher, but high rate performance and poor circulation, 10C capacity retention ratios only 72.1% recycle capacity holding in 300 weeks
Rate only reaches 81.7%；Comparative example 2 without CVD deposition nano-silicon, the coulombic efficiency for the first time of obtained negative material and follow it is bad
Better performances, but reversible capacity is too low for the first time, only 274.1mAh/g；Comparative example 3 is added without graphene, obtained negative material
First charge-discharge efficiency, high rate performance and cycling behavior be obviously deteriorated, first charge discharge efficiency only 87.6%, 10C rate capabilities keep
Rate only 73.6%, 300 weeks capacity retention ratios of cycle only reach 83.7%.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (8)
1. a kind of lithium ion battery nucleocapsid negative material, it is characterised in that：The negative material is nucleocapsid, kernel
For nano-silicon, nano lithium titanate and stannic oxide/graphene nano piece, wherein nano-silicon is attached to the surface of lithium titanate particle, is attached with
The lithium titanate particle of nano-silicon is evenly distributed between stannic oxide/graphene nano piece, and shell is organic cracking carbon-coating；The nanometer
The median particle diameter of silicon is 5~100nm；The median particle diameter of the nano lithium titanate is 1~500nm；The stannic oxide/graphene nano
The thickness of piece is 1~100nm；The thickness of organic cleaving layer is 0.1~5 μm.
2. lithium ion battery nucleocapsid negative material according to claim 1, which is characterized in that the negative material
In：The content of nano-silicon is 5wt%~40wt%, and the content of lithium titanate is 5wt%~40wt%, stannic oxide/graphene nano piece
Content is 1wt%~20wt%, and the content of organic cracking carbon-coating is 10wt%~60wt%；The median particle diameter of the negative material
It is 1~30 μm；The specific surface area of the negative material is 1~30m2/g；The powder body compacted density of the negative material be 0.1~
2.5g/cm3, preferably 0.5~2g/cm3。
3. a kind of preparation method of the lithium ion battery nucleocapsid negative material as described in claim 1 and 2, feature exist
In including the following steps：
(1) lithium titanate powder is placed in ball milling in ball mill, nanoscale lithium titanate particle is made；
(2) CVD deposition method is utilized, nano-silicon is deposited in nanoscale lithium titanate particle made from step (1), cathode material is obtained
Material precursor one；
(3) stannic oxide/graphene nano piece suspension is prepared；
(4) negative material presoma one made from step (2) stannic oxide/graphene nano piece made from step (3) is added to suspend
In liquid, composite mortar is obtained after high speed dispersion, then carry out atomization drying, obtain negative material presoma two；
(5) negative material presoma two made from step (4) is homogeneous compound with the progress of organic cracking carbon source, it is subsequently placed in reaction
In device, high temperature sintering obtains the negative material of nucleocapsid under atmosphere of inert gases.
4. the lithium ion battery according to claim 3 preparation method of nucleocapsid negative material, which is characterized in that institute
It states in step (1)：The median particle diameter of the lithium titanate powder is 1~50 μm, purity >=99.9%；The ball mill is selected from height
One kind in fast Ball-stirring mill, planetary ball mill, tube mill and sand mill, preferably sand mill；In the ball-grinding machine
The one kind of the material of ball milling pearl in stainless steel, agate, ceramics, zirconium oxide and hard alloy, a diameter of the 1 of the ball milling pearl
~10mm；In mechanical milling process, ratio of grinding media to material is (10~200):1, rotational speed of ball-mill is 50~2000rpm, and Ball-milling Time is 1~50h；
The median particle diameter of the nanoscale lithium titanate particle is 1~500nm.
5. the lithium ion battery according to claim 3 preparation method of nucleocapsid negative material, which is characterized in that institute
Stating step (2) is specially：The nano lithium titanate particle obtained in step (1) is added in CVD furnace internal-linings, inert gas is passed through
CVD furnace airs are excluded, until oxygen content≤300ppm, then with the heating rate of 1.0~5 DEG C/min, it is warming up to 400~
It 1000 DEG C, after 1~8h of roasting time, then is continually fed into organic silicon source gas and carries out chemical vapor deposition, when chemical vapor deposition
Between 0.5~5h, organic silicon source gas flow be 1~10L/min, then 1~5h of Isothermal sinter, makes silicon nanoparticle uniformly sink
Product obtains negative material presoma one in nanoscale lithium titanate particle；
Wherein, the organic silicon source gas is silane, dichlorosilane, trichlorosilane, silicon tetrachloride, one in ocratation
Kind or two or more combinations；The inert gas is at least one of nitrogen, helium, neon and argon gas.
6. the lithium ion battery according to claim 3 preparation method of nucleocapsid negative material, which is characterized in that institute
Stating step (3) is specially：Under conditions of ice-water bath, graphite is added in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, stirring is equal
It is even, potassium permanganate is then added, is warming up to 50~200 DEG C, is stirred to react 1~20h, graphite is made to be fully oxidized, generates oxidation
Graphite, then hydrogen peroxide is added in graphite oxide solution until there is no gases to generate, unreacted potassium permanganate is removed, and
It is cleaned 1~10 time with deionized water, the solution after cleaning is finally subjected to ultrasonic stripping, stannic oxide/graphene nano piece is made and suspends
Liquid；
Wherein, the concentrated sulfuric acid and the volume ratio of concentrated nitric acid mixing are 1 in mixed liquor:1；Every gram of graphite is in requisition for 10~40mL
Mixed liquor；The mass ratio of the graphite and potassium permanganate is 1:(1~5)；The thickness of the stannic oxide/graphene nano piece be 1~
100nm。
7. the lithium ion battery according to claim 3 preparation method of nucleocapsid negative material, which is characterized in that institute
Stating step (4) is specially：Negative material presoma one made from step (2) is added to graphene oxide made from step (3)
In nanometer sheet suspension, it is slowly stirred after 0.5~5h and imports in high speed dispersor, and be passed through inert gas, rotating speed is 1000~
12000rpm, 1~10h of high speed dispersion time, obtains finely dispersed composite mortar, and it is dry that composite mortar is then carried out atomization
It is dry, obtain negative material presoma two；
Wherein, the solid content of the compound slurry is 10~70wt%；The high speed dispersor is planetary ball mill, pipe mill
One kind in machine, type taper grinder, rod mill, homogenizer and sand mill；The inert gas is in nitrogen, helium, neon and argon gas
At least one；The hot-air inlets temperature of the atomization drying is 180~350 DEG C, and outlet temperature is 110~200 DEG C.
8. the lithium ion battery according to claim 3 preparation method of nucleocapsid negative material, which is characterized in that institute
It states in step (5)：The negative material presoma two is mixed with organic cracking carbon source, mixing quality ratio is 1:(0.1~5),
It is subsequently placed in VC mixing machines, adjusts 5~100Hz of frequency, mix at least 20min, be subsequently placed in reactor, be passed through indifferent gas
Body is warming up to 400~1000 DEG C, and heat preservation 0.5~8h postcoolings obtain the negative material of nucleocapsid to room temperature；
Wherein, organic cracking carbon source be pitch, epoxy resin, phenolic resin, furfural resin and acrylic resin in extremely
The grain size of few one kind, organic cracking carbon source is 1~20 μm；The inert gas is in nitrogen, helium, neon and argon gas
It is at least one；The reactor is one kind in vacuum drying oven, batch-type furnace, rotary furnace, roller kilns, pushed bat kiln and tube furnace.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841383A (en) * | 2019-04-26 | 2020-10-30 | 宁德时代新能源科技股份有限公司 | Negative electrode material production equipment |
| CN113948684A (en) * | 2020-07-15 | 2022-01-18 | 三星Sdi株式会社 | Negative active material and rechargeable lithium battery including the same |
| CN114314664A (en) * | 2021-11-30 | 2022-04-12 | 松山湖材料实验室 | Vanadium oxide coated carbide composite material and preparation method and application thereof |
| CN115020667A (en) * | 2022-06-24 | 2022-09-06 | 广东海洋大学 | Silicon-carbon composite negative electrode material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103311506A (en) * | 2013-06-25 | 2013-09-18 | 蒋涛 | Preparation method of silicon graphene-coated lithium titanate composite negative electrode material |
| CN104332613A (en) * | 2014-11-18 | 2015-02-04 | 东莞市翔丰华电池材料有限公司 | Lithium ion battery silicon-carbon composite negative material and its preparation method |
| CN104934608A (en) * | 2015-04-13 | 2015-09-23 | 青岛科技大学 | Preparation method of in-situ graphene coated lithium ion battery cathode material |
| CN107634212A (en) * | 2017-10-17 | 2018-01-26 | 深圳市贝特瑞新能源材料股份有限公司 | Multicomponent alloy composite negative pole material, preparation method and include the composite cathode material lithium ion battery |
| CN108365195A (en) * | 2018-02-06 | 2018-08-03 | 深圳市普锐能源科技有限公司 | A kind of lithium ion battery nucleocapsid negative material and preparation method thereof |
-
2018
- 2018-08-30 CN CN201811004804.3A patent/CN108807956A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103311506A (en) * | 2013-06-25 | 2013-09-18 | 蒋涛 | Preparation method of silicon graphene-coated lithium titanate composite negative electrode material |
| CN104332613A (en) * | 2014-11-18 | 2015-02-04 | 东莞市翔丰华电池材料有限公司 | Lithium ion battery silicon-carbon composite negative material and its preparation method |
| CN104934608A (en) * | 2015-04-13 | 2015-09-23 | 青岛科技大学 | Preparation method of in-situ graphene coated lithium ion battery cathode material |
| CN107634212A (en) * | 2017-10-17 | 2018-01-26 | 深圳市贝特瑞新能源材料股份有限公司 | Multicomponent alloy composite negative pole material, preparation method and include the composite cathode material lithium ion battery |
| CN108365195A (en) * | 2018-02-06 | 2018-08-03 | 深圳市普锐能源科技有限公司 | A kind of lithium ion battery nucleocapsid negative material and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841383A (en) * | 2019-04-26 | 2020-10-30 | 宁德时代新能源科技股份有限公司 | Negative electrode material production equipment |
| CN111841383B (en) * | 2019-04-26 | 2022-07-12 | 宁德时代新能源科技股份有限公司 | Negative electrode material production equipment |
| CN113948684A (en) * | 2020-07-15 | 2022-01-18 | 三星Sdi株式会社 | Negative active material and rechargeable lithium battery including the same |
| CN114314664A (en) * | 2021-11-30 | 2022-04-12 | 松山湖材料实验室 | Vanadium oxide coated carbide composite material and preparation method and application thereof |
| CN114314664B (en) * | 2021-11-30 | 2023-09-29 | 松山湖材料实验室 | Vanadium oxide coated carbide composite material and preparation method and application thereof |
| CN115020667A (en) * | 2022-06-24 | 2022-09-06 | 广东海洋大学 | Silicon-carbon composite negative electrode material and preparation method and application thereof |
| CN115020667B (en) * | 2022-06-24 | 2024-02-27 | 广东海洋大学 | Silicon-carbon composite anode material and preparation method and application thereof |
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