CN109428066A - Core-shell material and preparation method thereof, lithium ion battery negative material and lithium ion battery - Google Patents

Core-shell material and preparation method thereof, lithium ion battery negative material and lithium ion battery Download PDF

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Publication number
CN109428066A
CN109428066A CN201710761651.6A CN201710761651A CN109428066A CN 109428066 A CN109428066 A CN 109428066A CN 201710761651 A CN201710761651 A CN 201710761651A CN 109428066 A CN109428066 A CN 109428066A
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core
lithium
shell
layer
preparation
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林欢
刘孟
毕玉敬
秦银平
王德宇
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • 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
    • H01M4/36—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
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

This application discloses a kind of core-shell material and preparation method thereof, the core-shell material includes core and at least one layer of shell；The core includes lithium titanate class material；The shell includes at least one of lithium-containing oxides and/or at least one of other metal oxides；The core-shell material can improve the electric conductivity of electrode material as the negative electrode material of lithium ion battery；For effectively inhibiting the side reaction of electrode surface and electrolyte in lithium ion battery, it is good, forthright good, highly-safe again to have many advantages, such as cyclicity, and preparation process is simple, be suitble to large-scale production and application.

Description

Core-shell material and preparation method thereof, lithium ion battery negative material and lithium ion battery
Technical field
This application involves a kind of core-shell material and preparation method thereof, lithium ion battery negative material and lithium ion batteries, belong to In lithium ion battery material and field of cell preparation.
Background technique
With the rapid development of global industrial economy, the fossil energy that we are relied on is since its resource is limited and utilization rate The low sustainable development for having limited global economy and environment, the renewable and clean energy resource for finding substitution just become World Focusing Problem.Solar energy and wind energy are as renewable and clean energy resource the most abundant in natural environment, since there are peak valley fluctuation, poles for it Its use in existing power grid is limited greatly.Therefore, it is necessary to develop storage renewable energy source device to introduce smart grid；Its In, secondary lithium battery is since the advantages such as its high-energy density, long circulation life, low cost, safety are as electrochemistry storage Energy device is used widely in global energy storage technology.
In secondary lithium battery, negative electrode material is as one of its chief component, the direct shadow of the performance of material The performance of secondary lithium battery is rung.Lithium metal as optimal negative electrode material, due to its in charge and discharge process easily It generates Li dendrite and causes easily to explode in battery use process, safety is low, is generally not applied to commercial battery.And it passes The graphite cathode material of system discharge performance under high magnification is poor, limits its application in power battery, smart grid；Together When, graphite cathode material current potential in process of intercalation is lower, is also easy to produce Li dendrite, and there are some potential safety problemss.
Application of the lithium titanate of zero strain material spinelle type in lithium ion battery negative material receives extensive pass Note, long circulation life that it has and safety provide preferable application foundation for smart grid and power battery, are energy storage The important research direction of secondary lithium battery negative electrode material in technology.
It is found in current research, the conductivity of lithium titanate material is lower, the lithium titanate electrode material in cyclic process Surface and electrolyte occur side reaction and flatulence phenomenon occur, influence its high rate performance, lead to the decaying of battery capacity.Therefore, The lithium titanate material that research and development can be improved lithium titanate anode material conductivity, metatitanic acid lithium electrode surface is inhibited to react with electrolyte, It can effectively push lithium titanate battery in the application of energy storage and power battery field.
Summary of the invention
According to the one aspect of the application, a kind of core-shell material and preparation method thereof is provided, which can be effective Improve the conductivity of metatitanic acid lithium electrode, metatitanic acid lithium electrode surface inhibited react with electrolyte, improve the cycle performance of battery with again Rate performance.
The core-shell material includes core and at least one layer of shell；The core includes lithium titanate class material；The lithium titanate class material Material is selected from least one of the compound with chemical formula shown in Formulas I:
LipAxTiqO12Formulas I
Wherein, p+x+q=9；2≤p≤4,0≤x≤2,3≤q≤5, A are selected from least one of metallic element；
The shell includes at least one of lithium-containing oxides and/or at least one of other metal oxides；
The lithium-containing oxides is selected from least one of the compound with chemical formula shown in Formula II；
LiyMOzFormula II
Wherein, M represents metallic element, and valence state=2z of y+ metal M；
Other described metal oxides are selected from least one of the compound with chemical formula shown in formula III；
QaObFormula III
Wherein, Q represents metallic element, and a × metal Q valence state=2b；
Other described metal oxides corresponding reduction potential in lithium ion battery is lower than the reduction potential of lithium titanate.
Preferably, other described metal oxides have electro-chemical activity, can individually be used as negative electrode of lithium ion battery Material.
Preferably, the lithium-containing oxides is a kind of solid electrolyte, has the ability of transmission lithium ion, and cannot be with titanium Sour lithium forms doping.
Preferably, p+x+q=9 in the Formulas I；3≤p≤4,0≤x≤Isosorbide-5-Nitrae≤q≤5.
Preferably, p=4, q=5-x in the Formulas I.
Preferably, p=4-x/3, q=5-2x/3 in the Formulas I.
Preferably, p=4-x, q=5 in the Formulas I.
Preferably, in the Formulas I, x=1；A in Mg, Cr, Zn, Ga, Mn, Co, La, Nb, Mo, Ag, Al, Zr extremely Few one kind；
In the Formula II, M is selected from one of Ta, V, Ni, Bi, W, Sn, Sc, Ti, Nb；
In the formula III, Q is selected from one of Nb, Cu, Sn, Cr, Mo, Pb, Co, Fe, Mn, Bi.
Preferably, the lithium-containing oxides is selected from LiTaO3、LiVO2、LiNiO2、LiBiO3、Li2WO4、LiSnO2、 LiScO2、Li2TiO3、LiNbO3At least one of.
Preferably, other described metal oxides are selected from Nb2O5、CuO、Cu2O、SnO2、Cr2O3、MoO、PbO、Co3O4、 CoO、Fe3O4、Fe2O3、FeO、MnO2、Bi2O3At least one of.
It preferably, further include carbon-coating in the shell；The carbon-coating include graphite, soft carbon, hard carbon, in agraphitic carbon at least It is a kind of.
Preferably, the number of plies of the shell is 1,2,3,4 or 5 layer.
Preferably, the shell includes at least one layer of lithium-containing oxides and/or other at least one layer of metal oxides；Or
The shell includes at least one layer of lithium-containing oxides and/or other at least one layer of metal oxides and at least one layer of cladding Carbon-coating outside at least one layer of lithium-containing oxides and/or other at least one layer of metal oxides.
Preferably, the second particle particle size range of the core is 4 μm~15 μm, and the material shell thickness is 1nm- 500nm。
The second particle refers to: when crystal is very tiny, since the surface of crystal grain can very greatly, and tiny crystal grain Between be easy to be combined together due to weak interaction force, cause to reunite between crystal grain, that is, many a tiny crystalline substances Grain is united, and bigger second particle is formed.
The preparation method of the core-shell material, comprising:
(1) lithium titanate class material is obtained；
(2) contact by lithium titanate class material with the raw material for preparing Composite Shell, is coated；
The shell includes at least one layer of lithium-containing oxides and/or other at least one layer of metal oxides；Or the shell packet It includes at least one layer of lithium-containing oxides and/or other at least one layer of metal oxides and at least one layer is coated at least one layer containing lithia Carbon-coating outside compound and/or other at least one layer of metal oxides；
When the number of plies of Composite Shell >=2, then successively coated according to the direction far from core.
Preferably, the lithium titanate class material is bought by commercial sources.
Preferably, the preparation method of the lithium titanate class material includes:
Lithium source, titanium source are well-dispersed in dehydrated alcohol, it is dry, then under protective atmosphere, 400~1100 DEG C of reactions 4~24 hours to get；Or
The raw material of lithium source, titanium source and doped chemical M are well-dispersed in dehydrated alcohol, it is dry, then in protection gas Under atmosphere, 400~1100 DEG C reaction 4~24 hours to get.
Preferably, the raw material of the doped chemical M in the corresponding oxide of M, hydroxide, metal salt at least It is a kind of.
Preferably, the otide containing lighium nitride layer the preparation method comprises the following steps: material to be covered is mixed with salt containing M and regulation system PH value obtains the presoma for the hydroxide for being coated with M；Presoma is mixed with lithium source, high temperature sintering to get；
Other metal oxide layers the preparation method comprises the following steps: material to be covered is mixed with salt containing Q and regulation system pH, Obtain the presoma for the hydroxide for being coated with Q, high temperature sintering presoma to get；Or by the oxide of material to be covered and Q And/or after the hydroxide mixed grinding of Q, high temperature sintering to get；
The carbon-coating the preparation method comprises the following steps: material to be covered is mixed with carbon source after, high temperature sintering to get.
Preferably, the salt containing M in the corresponding chloride of M, carbonate, acetate, formates, citrate extremely Few one kind.
Preferably, the lithium source in lithium carbonate, lithium hydroxide, lithium acetate, lithium formate, three lithium of citric acid at least one Kind.
Preferably, the salt containing Q in the corresponding chloride of Q, carbonate, acetate, formates, citrate extremely Few one kind.
The material to be covered be core, core be coated at least one layer of otide containing lighium nitride layer material, core be coated with to Material, the core of few one layer of other metal oxide layer be coated at least one layer of otide containing lighium nitride layer material and it is at least one layer of its At least one of the material of his metal oxide layer.
The regulation system pH is that the pH of solution is adjusted to 8~12 using ammonium hydroxide.
Preferably, the preparation method of the otide containing lighium nitride layer, the preparation method of other metal oxide layers, the system of carbon-coating In Preparation Method, the temperature of high temperature sintering independently selected from 400~1100 DEG C, time of high temperature sintering independently selected from 2~28h, High temperature sintering atmosphere is independently selected from least one of high-purity argon gas, oxygen, argon hydrogen gaseous mixture.
Preferably, the mixed uniformly mode includes: that solid material is mixed in solvent, is then dried either The solution of solid material directly mixes.
Preferably, the carbon source be selected from acetylene black, superconduction carbon black, Ke Qinhei, graphene, sucrose, glucose, succinic acid, At least one of citric acid, acetic acid.
Preferably, the temperature of high temperature sintering is 400~900 DEG C, and the time of high temperature sintering is 3~10 hours.
As a kind of specific embodiment, the core-shell material preparation method, comprising:
(1) by lithium titanate class material and Zr (OH)4、Al(OH)3、Mg(OH)2、Fe(OH)3、Zn(OH)2、Bi(OH)5、Co (OH)2、Ni(OH)2、Mn(OH)2At least one of mixing, and/or and Nb2O5、ZrO2、Ta2O5、MoO、PbO、V2O5、TiO2In At least one mixing, mixing and ball milling 1~10 hour in alcohol dispersant；Wherein, the hydroxide and oxide are The presoma of shell substance；
(2) by the mixture after ball milling under protective atmosphere 400~1100 DEG C pyroreaction 2~28 hours, obtain surface Coat the presoma of transition zone；
(3) by the presoma and lithium source and/or carbon source of surface cladding transition zone, in alcohol dispersant mixing and ball milling 1~ 10 hours；
Wherein, lithium source is selected from least one of lithium carbonate, lithium hydroxide, lithium acetate, lithium formate, three lithium of citric acid；
Wherein, carbon source be selected from acetylene black, superconduction carbon black, Ke Qinhei, graphene, sucrose, glucose, succinic acid, citric acid, At least one of acetic acid；
(4) by mixed mixture under protective atmosphere 400~900 DEG C pyroreaction 2~28 hours, obtain with table The lithium titanate of face composite layer, i.e. lithium ion battery negative material.
According to the another aspect of the application, a kind of lithium ion battery negative material, the negative electrode of lithium ion battery material are provided At least one of the core-shell material that material is prepared containing at least one of above-mentioned core-shell material and/or the above method.
The another aspect of the application, provides a kind of lithium ion battery, and it includes above-mentioned lithium ion battery negative materials.
The preparation method of lithium ion battery includes: in the application
(i) by negative electrode material respectively with conductive agent acetylene black, binder Kynoar (PVDF) in N-methyl pyrrolidines It is mixed evenly in ketone (NMP) solution；Preferably, the mass ratio of negative electrode material, acetylene black and binder is 90:5:5；
(ii) slurry being mixed evenly is coated on aluminium foil, it is dry, negative electrode of lithium ion battery is made.
It (iii) the use of above-mentioned pole piece is cathode, using lithium anode as to electrode, electrolyte uses 1mol/L hexafluoro phosphorus The ethylene carbonate of sour lithium and the solution of dimethyl carbonate, isolated material, assembling obtain lithium ion battery.
The beneficial effect that the application can generate includes:
1) core-shell material shell provided herein is uniform, and thickness is controllable.
2) core-shell material provided herein has surface coating layer, plays good guarantor to core
Shield effect.
3) preparation method of core-shell material provided herein is simple, is suitble to large-scale production and application.
4) core-shell material provided herein is used as lithium ion battery negative material, can improve electrode
Material conductivity, the side reaction for effectively inhibiting electrode surface and electrolyte, good with cyclicity,
The advantages that forthright good, conductivity is high, safety is good again.
Detailed description of the invention
Fig. 1 is the high rate performance comparison diagram of sample DC1 and C1.
Fig. 2 is cycle performance comparison diagram at 55 DEG C of sample DC1 and C3.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, the raw material in embodiments herein and catalyst are bought by commercial sources.
Analysis method is as follows in embodiments herein:
High rate performance is carried out using blue electrical measurement test system CT2001A and cycle performance data are analyzed.
The partial size of material is observed using U.S. FEI QUANTA 250FEG field emission scanning electron microscope in the application.
The preparation of 1 core material of embodiment
Core material Li4Zr0.15Ti4.85O12Preparation
2:0.15:4.85 weighs lithium carbonate, zirconium oxide, titanium dioxide mixing respectively in molar ratio, is point with dehydrated alcohol Powder is placed in ball mill with 480 revs/min, ball milling 4 hours, and the mixture that ball milling is gone out is done in 80 DEG C of vacuum oven After dry 6 hours, taking-up is ground into powder, is put into tube furnace and is passed through high-purity argon gas pyroreaction, with the rate of 5 DEG C/min 800 DEG C are warming up to, 1200min is kept the temperature, cooled to room temperature obtains core material Li4Zr0.15Ti4.85O12, partial size is 10 μm Left and right.
Core material Li4Ti5O12Preparation
2:5 is mixed after weighing lithium carbonate and titanium dioxide respectively in molar ratio, using dehydrated alcohol as dispersing agent, will be mixed Object is placed in ball mill with 480 revs/min, ball milling 6 hours, and the mixture after ball milling is dried 8 hours in 80 DEG C of drying box； By the powder after drying, grinding sufficiently, is placed in tube furnace, is passed through high-purity argon gas high-temperature calcination, is heated up with the rate of 5 DEG C/min To 750 DEG C of calcining 900min；Cooled to room temperature obtains core material Li4Ti5O12, it is labeled as D1#, partial size is 10 μm of left sides It is right.
Core material Li3.95Al0.15Ti4.9O12Preparation
The same Li of basic preparation step4Zr0.15Ti4.85O12, the difference is that, change zirconium oxide into equivalent molar number Aluminium oxide.Meet lithium carbonate, aluminium oxide, titanium dioxide molar ratio be 1.975:0.075:4.9.
2 core-shell material Li of embodiment4Zr0.15Ti4.85O12/Bi2O3/SnO2Preparation
Prepare core material Li4Zr0.15Ti4.85O12, tier I shell is Bi2O3, tier ii shell be SnO2Core-shell material.
Weigh the Li of preparation4Zr0.15Ti4.85O12- 9.314g, Bi (OH)3- 0.3258g, it is molten that dehydrated alcohol is added in mixing In agent, 480 revs/min ball milling 4 hours, the mixture that ball milling is gone out drying 6 in 80 DEG C of vacuum oven are small in the ball mill Shi Hou, taking-up are ground into powder, are put into tube furnace and are passed through high-purity argon gas pyroreaction, are heated up with the rate of 5 DEG C/min To 600 DEG C, 180min is kept the temperature, cooled to room temperature obtains the presoma P1 with surface cladding transition zone；
Weigh presoma P1-9.5326, SnO2- 0.1943g is mixed into anhydrous ethanol solvent, in the ball mill 480 revs/min ball milling 4 hours, the mixture that ball milling is gone out in 80 DEG C of vacuum oven after dry 6 hours, ground by taking-up It clays into power, is put into tube furnace and is passed through high-purity argon gas pyroreaction, be warming up to 500 DEG C with the rate of 5 DEG C/min, heat preservation 180min；Cooled to room temperature is obtained with Bi2O3/SnO2The Li of surface composite layer4Zr0.15Ti4.85O12Core-shell material, mark It is denoted as 1#。
3 core-shell material Li of embodiment4Ti5O12/LiNbO3/Co3O4Preparation
Preparing core material is Li4Ti5O12, tier I shell is LiNbO3, tier ii shell be Co3O4Core-shell material.
Weigh Li4Ti5O12200ml deionized water is added in -45.911g, stirs to form dispersion solution；Prepare 1mol/L Ammonia spirit weighs niobium chloride 34.083g, and 70ml deionized water dissolving is added；The niobium chloride solution of preparation is added Li4Ti5O12Dispersion liquid in, after addition, with ammonium hydroxide adjust pH to 8.0, after being filtered, being washed three times, at 100 degrees Celsius It is dried in drying box, obtains surface cladding Nb (OH)4Presoma P2.
Above-mentioned presoma P2-47.688g is weighed, is mixed according to the molar ratio of Nb:Li for 1:1.02 with lithium hydroxide It is even, 850 DEG C air calcination 4 hours, obtain surface cladding LiNbO3Li4Ti5O12。
Weigh Co (CH3COO)2·4H2O -5.893g is dissolved in 30ml deionized water；The LiOH for preparing 4mol/L is molten Liquid and 1mol/L ammonia spirit.
By Co (CH3COO)2The LiOH and ammonia spirit of solution and 4mol/L are added to the dispersion solution of presoma P2 simultaneously In, by Co (OH)2It is deposited in the surface presoma P2, controls pH=12.It filtered, washed, obtain compound precursor after 100 DEG C of dryings Body P3 under oxygen atmosphere, is warming up to 480 DEG C with the rate of 5 DEG C/min, keeps the temperature 360min by the precursor in tube furnace；From It is so cooled to room temperature, obtains with LiNbO3/Co3O4The Li of surface composite layer4Ti5O12Core-shell material is labeled as 2#。
4 core-shell material Li of embodiment4Ti5O12/LiNbO3/Co3O4The preparation of/C
Preparing core material is Li4Ti5O12, tier I shell is LiNbO3, tier ii shell be Co3O4, layer III shell be C Core-shell material.
Weigh the core-shell material 2 that 20g embodiment 3 is prepared#Li4Ti5O12/LiNbO3/Co3O4, it is according to cladding carbon amounts 10wt% is uniformly mixed after weighing sucrose.
Uniform mixture is placed in tube furnace, in argon hydrogen gaseous mixture, is warming up to 600 DEG C with the rate of 5 DEG C/min, Keep the temperature 480min；Cooled to room temperature obtains having for LiNbO3/Co3O4The Li of the surface composite layer of/C4Ti5O12Nucleocapsid material Material is labeled as 3#。
The preparation of 5 lithium ion battery of embodiment
By the negative electrode material of preparation respectively with conductive agent acetylene black, binder Kynoar (PVDF) in N-methyl pyrroles It is mixed evenly in alkanone (NMP) solution, the mass ratio of negative electrode material, acetylene black and binder is 90:5:5.
The slurry being mixed evenly is coated on aluminium foil, it is 12 hours dry in 120 DEG C of vacuum ovens, lithium is made Ion battery cathode.
It the use of above-mentioned pole piece is cathode, using lithium anode as to electrode, electrolyte uses 1mol/L lithium hexafluoro phosphate Ethylene carbonate and dimethyl carbonate solution, the PP-PE diaphragm of 20 μ m-thicks is assembled into CR2032 coin shape lithium-ion electric Pond.
Directly adopt gained Li in embodiment 14Ti5O12As negative electrode material, and the lithium being prepared according to the above method from Sub- battery is labeled as DC1；
With sample 1#For negative electrode material, the lithium ion battery being prepared according to the above method is labeled as C1；
With sample 2#For negative electrode material, the lithium ion battery being prepared according to the above method is labeled as C2；
With sample 3#For negative electrode material, the lithium ion battery being prepared according to the above method is labeled as C3.
6 performance of embodiment and characterization test
(1) high rate performance is tested
The step of multiplying power is tested and condition: (at room temperature)
The button cell that C1 and DC1 sample assembly is completed respectively carries out charge and discharge electrical measurement on blue electric charge-discharge test instrument Examination, theoretical capacity 175mAh/g.
Steps are as follows:
Electric discharge: 0.1C, until 1V；Charging: 0.1C, until 2.5V；Circulation 5 weeks；
Electric discharge: 0.5C, until 1V；Charging: 0.5C, until 2.5V；Circulation 5 weeks；
Electric discharge: 1C, until 1V；Charging: 1C, until 2.5V；Circulation 5 weeks；
Electric discharge: 2C, until 1V；Charging: 2C, until 2.5V；Circulation 5 weeks；
Electric discharge: 5C, until 1V；Charging: 5C, until 2.5V；Circulation 5 weeks；
Electric discharge: 0.1C, until 1V；Charging: 0.1C, until 2.5V；Circulation 10 weeks.
Pass through comparison (shown in Fig. 1), it can be seen that the lithium titanate anode material with surface composite layer is on high rate performance It is more stable compared with lithium titanate surface.
(2) cycle performance is tested
The button cell being completed carries out charge-discharge test on blue electric charge-discharge test instrument, and voltage range is 1~ 2.5V, charging and discharging currents density are 17.5mA/g.
C3 and DC1 is subjected to 250 cycle of charge and discharge cycles at 55 DEG C, charging and discharging currents density is 17.5mA/g.Pass through It compares (shown in Fig. 2), it can be seen that the lithium titanate anode material in embodiment 1 with surface composite layer is obvious on cycle performance It is improved and relatively stable.
Sample 2#Test result and sample 1#With 3#Result it is similar, illustrate to make with core-shell material provided herein For negative electrode material, have the advantages that cyclicity it is good, again it is forthright it is good, conductivity is high.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to Case study on implementation is imitated, is belonged in technical proposal scope.

Claims (10)

1. a kind of core-shell material, which is characterized in that the core-shell material includes core and at least one layer of shell；
The core includes lithium titanate class material；The lithium titanate class material is in the compound with chemical formula shown in Formulas I It is at least one:
LipAxTiqO12Formulas I
Wherein, p+x+q=9；2≤p≤4,0≤x≤2,3≤q≤5, A are selected from least one of metallic element；
The shell includes at least one of lithium-containing oxides and/or at least one of other metal oxides；
The lithium-containing oxides is selected from least one of the compound with chemical formula shown in Formula II；
LiyMOzFormula II
Wherein, M represents metallic element, and valence state=2z of y+ metal M；
The lithium-containing oxides is a kind of solid electrolyte, and has the ability of transmission lithium ion；
Other described metal oxides are selected from least one of the compound with chemical formula shown in formula III；
QaObFormula III
Wherein, Q represents metallic element, and a × metal Q valence state=2b；
Other described metal oxides corresponding reduction potential in lithium ion battery is lower than the reduction potential of lithium titanate.
2. core-shell material according to claim 1, which is characterized in that in the Formulas I, x=1；A be selected from Mg, Cr, Zn, Ga, At least one of Mn, Co, La, Nb, Mo, Ag, Al, Zr；
In the Formula II, M is selected from one of Ta, V, Ni, Bi, W, Sn, Sc, Ti, Nb；
In the formula III, Q is selected from one of Nb, Cu, Sn, Cr, Mo, Pb, Co, Fe, Mn, Bi；
Preferably, the lithium-containing oxides is selected from LiTaO3、LiVO2、LiNiO2、LiBiO3、Li2WO4、LiSnO2、LiScO2、 Li2TiO3、LiNbO3At least one of；
Preferably, other described metal oxides are selected from Nb2O5、CuO、Cu2O、SnO2、Cr2O3、MoO、PbO、Co3O4、CoO、 Fe3O4、Fe2O3、FeO、MnO2、Bi2O3At least one of.
3. core-shell material according to claim 1 or 2, which is characterized in that further include carbon-coating in the shell；The carbon-coating packet Include at least one of graphite, soft carbon, hard carbon, agraphitic carbon.
4. core-shell material according to any one of claims 1 to 3, which is characterized in that the number of plies of the shell be 1,2,3,4 or 5 layers；
Preferably, the shell includes at least one layer of lithium-containing oxides and/or other at least one layer of metal oxides；Or
The shell includes at least one layer of lithium-containing oxides and/or other at least one layer of metal oxides and at least one layer be coated on to Carbon-coating outside few one layer of lithium-containing oxides and/or other at least one layer of metal oxides.
5. core-shell material according to claim 1, which is characterized in that the shell with a thickness of 1nm-500nm.
6. a kind of preparation method of the core-shell material as described in any one of claim 1 to 5, comprising:
(1) lithium titanate class material is obtained；
(2) lithium titanate class material is contacted with the raw material for preparing shell, is coated；
The shell includes at least one layer of lithium-containing oxides and/or other at least one layer of metal oxides；Or the shell includes extremely Few one layer of lithium-containing oxides and/or other at least one layer of metal oxides and at least one layer are coated at least one layer of lithium-containing oxides And/or the carbon-coating outside other at least one layer of metal oxides；
When the number of plies of shell >=2, then successively coated according to the direction far from core.
7. the preparation method of core-shell material according to claim 6, which is characterized in that the preparation of the otide containing lighium nitride layer Method are as follows: material to be covered is mixed to simultaneously regulation system pH value with salt containing M, obtains the presoma for the hydroxide for being coated with M；It will Presoma is mixed with lithium source, high temperature sintering to get；
Other metal oxide layers the preparation method comprises the following steps: material to be covered is mixed with Q salt and regulation system pH, wrapped Be covered with the presoma of the hydroxide of Q, high temperature sintering presoma to get；Or by the oxide and/or Q of material to be covered and Q Hydroxide mixed grinding after, high temperature sintering to get；
The carbon-coating the preparation method comprises the following steps: material to be covered is mixed with carbon source after, high temperature sintering to get；
The material to be covered is that core, core are coated with material, the core of at least one layer of otide containing lighium nitride layer and are coated at least one Material, the core of other metal oxide layers of layer are coated with the material and other at least one layer of gold of at least one layer of otide containing lighium nitride layer Belong at least one of the material of oxide skin(coating).
8. the preparation method of core-shell material according to claim 7, which is characterized in that the preparation of the otide containing lighium nitride layer Method, the preparation method of other metal oxide layers, in the preparation method of carbon-coating, the temperature of high temperature sintering is independently selected from 400 ~1100 DEG C, time of high temperature sintering independently selected from 2~28h, high temperature sintering atmosphere independently selected from high-purity argon gas, oxygen, At least one of argon hydrogen gaseous mixture.
9. a kind of lithium ion battery negative material, which is characterized in that the lithium ion battery negative material contain claim 1 to It at least one of 5 described in any item core-shell materials and/or is prepared according to any one of claim 6 to 8 the method At least one of core-shell material.
10. a kind of lithium ion battery, which is characterized in that include lithium ion battery negative material as claimed in claim 9.
CN201710761651.6A 2017-08-30 2017-08-30 Core-shell material and preparation method thereof, lithium ion battery negative material and lithium ion battery Pending CN109428066A (en)

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Application publication date: 20190305