CN109713235A - A kind of sub- composite material and preparation method of conduction diversion, modified electrode material and energy storage device - Google Patents
A kind of sub- composite material and preparation method of conduction diversion, modified electrode material and energy storage device Download PDFInfo
- Publication number
- CN109713235A CN109713235A CN201711009717.2A CN201711009717A CN109713235A CN 109713235 A CN109713235 A CN 109713235A CN 201711009717 A CN201711009717 A CN 201711009717A CN 109713235 A CN109713235 A CN 109713235A
- Authority
- CN
- China
- Prior art keywords
- diversion
- sub
- composite material
- conduction
- conductive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The embodiment of the invention provides a kind of sub- composite materials of conductive diversion, including conductive component and lead ion component, the conductive component is chemically bound together with the ion component of leading, the conductive component includes carbon material, the carbon material includes pure phase carbon material or the carbon material containing doped chemical, the diversion subgroup point includes fast-ionic conductor, the conduction sub- composite material of diversion has conductive subchannel and diversion subchannel simultaneously, and the conduction subchannel is coupled with the diversion subchannel.The sub- composite material of conduction diversion is provided simultaneously with high electronics conduction and high ion-conductivity energy, and stable structure, it is applied to the modification of electrode material, maximizing plays the energy density of electrode material itself, and improves the long circulating stability and safety of battery.The embodiment of the invention also provides the preparation methods of the sub- composite material of conduction diversion, and modified electrode material based on the sub- composite material of conduction diversion and preparation method thereof and energy storage device.
Description
Technical field
The present invention relates to technical field of lithium ion secondary, more particularly to a kind of sub- composite material of conductive diversion and its
Preparation method and a kind of modified electrode material and preparation method thereof and energy storage device.
Background technique
Lithium ion secondary battery is used widely in fields such as consumer electronics, electric vehicle, communications, with people couple
The growth of the long continuation of the journey demand of product, high-energy density electrode material of new generation such as silicium cathode, high pressure lithium cobaltate cathode, nickelic high pressure
NMC anode is paid close attention to by industry.
And on the one hand electrode material needs to have good ionic conductivity as the main part for playing energy storage function,
So that the lithium ion of deintercalation in electrode material is quickly transmitted and enter electrolyte in the electrodes, migrates to another pole, electrochemistry occurs
Reaction；On the other hand good electronic conductivity is needed to have, exports electronics in time to external circuit and form electric current, guarantees electricity
The low resistance of pole material reduces battery polarization, reduces fever, improves safety.Currently, in order to improve leading for electrode material simultaneously
Electricity and ionic nature is led, mainly electrode material is handled using following technological means: while using conductive material and leading
Ionic material jacketed electrode material, but conductive material and the sub- storeroom of diversion are mutually indepedent, without strong interaction.
However due in the generally existing charge and discharge process of high-energy density electrode material material deformation it is big, structural unstable
Problem.Therefore, as shown in Figure 1 (1 is electrode material in figure, and 2 be conductive material, and 3 be to lead ionic material), while using conductive
Property material and lead ionic material high-energy density electrode material handled according to above-mentioned existing way, in battery charge and discharge repeatedly
In electric process, conductive material and the sub- storeroom of diversion are generated due to not having strong interaction in electrode material structure change
Be separated from each other under mechanical force, cannot keep conductive diversion it is parallel be continuously turned on circuit.It is since battery plays energy storage function
Displacement, the destruction of any access will lead to the Local enrichment of electronics or ion and shadow based on electronics and while ion
Ring chemical property play, cause the internal resistance of cell increase, heat dissipation is obstructed, battery temperature increases suddenly, bring security risk.
Summary of the invention
In consideration of it, being provided simultaneously with high electronics conduction the embodiment of the invention provides a kind of sub- composite material of conductive diversion
With high ion-conductivity energy, and stable structure is applied to the modification of electrode material, and maximizing plays electrode material
The energy density of itself, and the long circulating stability and safety of battery are improved, to solve existing electrode material since surface is set
The conductive material set and ionic material is led between the two without strong interaction, two components are mutually de- easily in battery charge and discharge process
From or destroy, lose the continuity of perforation, so as to cause electrode material electronic conductivity and ionic conductivity reduce, electrode material
The problem of material internal resistance increases suddenly, and cycle performance and volumetric properties decline.
Specifically, first aspect of the embodiment of the present invention provides a kind of sub- composite material of conductive diversion, including conductive component
With lead ion component, the conductive component is chemically bound together with the ion component of leading, the conductive component packet
Carbon material is included, the carbon material includes pure phase carbon material or the carbon material containing doped chemical, and the diversion subgroup point includes fast
Ion conductor, the conduction sub- composite material of diversion have conductive subchannel and diversion subchannel, the conduction subchannel simultaneously
It is coupled with the diversion subchannel.
Wherein, the carbon material includes pure phase carbon material or the carbon material containing doped chemical.Specifically, the carbon material
Including one of fullerene, carbon nanotube, carbon fiber, graphene, graphite alkene, active carbon and porous carbon or a variety of.It is described to mix
Miscellaneous element include O, N, B, F, Cl, Co, Fe, Mn, Ni, Au, Cu, Zn, Al, Mg, Pt, Pd, La, Cr, Ge, Pb, Se, Ag, W, Ti,
One of P and Zr or a variety of.
Wherein, the fast-ionic conductor includes one of oxide type solid electrolyte, sulfide type solid electrolyte
Or it is a variety of.Specifically, the oxide type solid electrolyte includes crystalline state Ca-Ti ore type solid electrolyte, crystalline state NASICON type
Solid electrolyte, crystalline state LISICON type solid electrolyte, Garnet-type solid electrolyte, glassy oxide type solid state electrolysis
One of matter is a variety of；The sulfide type solid electrolyte includes crystalline state sulfide type solid electrolyte, glassy state vulcanization
One of object type solid electrolyte is a variety of.
Wherein, when the carbon material is pure phase carbon material, the chemical bond includes X-C key, one of Y-C key or more
Kind, when the carbon material is the carbon material containing doped chemical, the chemical bond includes X-C key, Y-C key, X-Z key, Y-Z key
One of or it is a variety of, wherein X is the element that electronegativity is more than or equal to carbon, and Y is metal or metalloid element, and Z is described contains
Doped chemical in the carbon material of doped chemical.Specifically, the X include one of C, N, O, S, B, F, Cl, Br, I, Se or
It is a variety of, the Y include Li, Na, K, Mg, Ca, Al, In, Pb, V, Cr, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, Si, Ga,
One of Sn, Ti, V, Zn, Zr, Ge or a variety of, the Z include O, N, B, F, Cl, Co, Fe, Mn, Ni, Au, Cu, Zn, Al,
One of Mg, Pt, Pd, La, Cr, Ge, Pb, Se, Ag, W, Ti, P and Zr or a variety of.
The conductive component accounts for the 0.1%-70% of the sub- composite material gross mass of the conductive diversion.
The sub- composite material of conductive diversion that first aspect of the embodiment of the present invention provides, be provided simultaneously with the conduction of high electronics and it is high from
Sub- conductive performance, and stable structure, are applied to the modification of electrode material, and maximizing plays electrode material itself
Energy density, and improve the long circulating stability and safety of battery.
Correspondingly, second aspect of the embodiment of the present invention provides a kind of preparation method of the sub- composite material of conductive diversion, packet
Include following steps:
Conductive component is provided and leads ion component, the sub- composite wood of conductive diversion is prepared using the first chemically composited mode
Material；The conductive component includes carbon material, and the carbon material is the carbon material containing doped chemical, and the diversion subgroup point includes
Fast-ionic conductor；
Or conductive component is provided, and diversion subgroup is provided and divides synthesis material, it is prepared into using the second chemically composited mode
To the sub- composite material of conductive diversion；The conductive component includes carbon material, and the carbon material includes pure phase carbon material or containing mixing
The carbon material of miscellaneous element；
Or provide and lead ion component, and conductive component is provided and prepares raw material, it is prepared into using the chemically composited mode of third
To the sub- composite material of conductive diversion；
The conduction sub- composite material of diversion includes conductive component and leads ion component, the conductive component and the diversion
Subgroup point is chemically bound together, and the conduction sub- composite material of diversion has conductive subchannel and diversion logical simultaneously
Road, the conduction subchannel are coupled with the diversion subchannel.
Wherein, the described first chemically composited mode includes high-energy ball milling method, high temperature fusion casting.The second chemically composited side
Formula and the chemically composited mode of the third are independently selected from chemical vapour deposition technique, vacuum heat deposition method, magnetron sputtering method, colloidal sol
Gel method, microwave process for synthesizing, hydro-thermal method, solvent-thermal method, liquid-phase precipitation method, high-energy ball milling method, high temperature fusion casting, molecular beam epitaxy
One of growth method, laser ablation and chemical etching method are a variety of.
The preparation method for the sub- composite material of conductive diversion that second aspect of the embodiment of the present invention provides, simple process.
The embodiment of the invention also provides a kind of modified electrode materials, including electrode material, and are distributed in the electrode
Material internal or the sub- composite material of conductive diversion for being coated on the electrode material surface, the electrode material includes positive-active
Material or negative electrode active material, the conduction sub- composite material of diversion is conductive diversion described in first aspect of the embodiment of the present invention
Sub- composite material.
Wherein, the quality of the sub- composite material of the conductive diversion accounts for the 0.01%- of the modified electrode material gross mass
30%.
The electrode material includes block materials, primary particle or second particle, the conduction sub- composite material of diversion point
Cloth is in the inside of the block materials, or is coated on the primary particle or the second particle surface.
The positive electrode active materials include LiFePO 4 material, cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickel cobalt manganese
Sour lithium, nickel cobalt lithium aluminate, nickel ion doped, rich lithium class positive electrode, iron manganese phosphate for lithium, sulphur, sulfur compound, ferric sulfate lithium, fluorine phosphorus
One of sour lithium, fluorophosphoric acid vanadium lithium, fluorophosphoric acid iron lithium are a variety of；The negative electrode active material include graphite, hard carbon, silicon, germanium,
One of tin, stannic oxide, antimony oxide, antimony carbon composite, tin antimony composite material, lithium titanate are a variety of.
In the modified electrode material, the conduction sub- composite material of diversion constructs to form three-dimensional conductive diversion sub-network.
Modified electrode material provided in an embodiment of the present invention is provided simultaneously with high electronics conduction and high ion-conductivity energy, and
Conductive diversion sub-network structure is stablized, and maximizing plays the energy density of bulk electrode material, extends the continuous of electronic product
ETS estimated time of sailing；Its Low ESR will also reduce battery-heating, be conducive to battery long circulating stability, promote service life and the peace of electronic product
Entirely, to improve electronic product whole competitiveness.
Correspondingly, the embodiment of the invention also provides a kind of preparation methods of modified electrode material, comprising the following steps:
It takes electrode material synthesis material or directly takes electrode material, and take as described in first aspect of the embodiment of the present invention
The conductive sub- composite material of diversion, is prepared modified electrode material, the electrode by the way of physical blending or chemical crosslinking
Material includes positive electrode active materials or negative electrode active material.
The physical blending or the mode of chemical crosslinking include solution-deposition method, vapour deposition process, vacuum heat deposition method, magnetic
Control one of sputtering method, sol-gal process, microwave process for synthesizing, hydro-thermal method, solvent-thermal method, high-temperature sintering process, high-energy ball milling method
Or it is a variety of.
The embodiment of the invention also provides a kind of energy storage device, including anode, cathode, diaphragm and electrolyte, the anodes
And/or the cathode includes the above-mentioned modified electrode material of the embodiment of the present invention, and in the energy storage device charge and discharge process, institute
Stating has the continuous conductive subchannel of perforation and leads between the electrode material of modified electrode material and the sub- composite material of conductive diversion
Ion channel, the conduction subchannel and the diversion subchannel composition that is coupled are continuously turned on circuit.The energy storage device packet
Include lithium ion battery, sodium-ion battery, Magnesium ion battery, aluminium ion battery or supercapacitor.
Detailed description of the invention
Fig. 1 is existing while using conductive material and leading electrode material that ionic material is handled in electrode material sheet
Surface composition of the body after deformation occurs changes schematic diagram；
Fig. 2 is the schematic diagram that graphene and fast-ionic conductor form chemical bonding in embodiment of the present invention；
Fig. 3 is the structure that the conductive sub- composite material of diversion is distributed in bulk electrode material internal in an embodiment of the present invention
Schematic diagram；
Fig. 4 is that the conductive sub- composite material of diversion is coated on electrode material primary particle surface in an embodiment of the present invention
Structural schematic diagram；
Fig. 5 is that the conductive sub- composite material of diversion is coated on electrode material second particle surface in an embodiment of the present invention
Structural schematic diagram；
Fig. 6 is surface composition of the modified electrode material provided in an embodiment of the present invention after deformation occurs in electrode material itself
Change schematic diagram；
Fig. 7 is the morphology characterization for the lithium cobaltate cathode material that graphene/LATP that the embodiment of the present invention 6 is prepared is modified
Figure；
Fig. 8 is the morphology characterization figure of the lithium cobaltate cathode material of comparative example of the present invention；
Fig. 9 is the XPS characterization for the lithium cobaltate cathode material that graphene/LATP that the embodiment of the present invention 6 is prepared is modified
Figure；
Figure 10 is the XPS characterization for the lithium cobaltate cathode material that graphene/LATP that the embodiment of the present invention 6 is prepared is modified
Figure.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, is illustrated to the embodiment of the present invention.
The embodiment of the invention provides a kind of conductive sub- composite material of diversion, including conductive component and ion component is led, institute
It states conductive component to be chemically bound together with the ion component of leading, the conductive component includes carbon material, the carbon
Material includes pure phase carbon material or the carbon material containing doped chemical, and the diversion subgroup point includes fast-ionic conductor, described to lead
Conductance ion composite material has conductive subchannel and diversion subchannel, the conduction subchannel and the diversion subchannel simultaneously
It is coupled.
In embodiment of the present invention, it is described conduction subchannel and the diversion subchannel be coupled refer to conductive subchannel with
Diversion subchannel occurs parallel.When the sub- composite material of conductive diversion is applied to anode or cathode, in battery system charge and discharge
In electric process, due to the sub- composite material of conductive diversion conductive component and lead the strong phase interaction between ion component with chemical bond
With, therefore even if conductive subchannel still is able to phase coupling with diversion subchannel in the case where electrode material structure generates variation
Merging rows occur, and ion and electronics can be obtained simultaneously by the conductive subchannel that is coupled with the diversion subchannel suitable
Benefit transmission, to guarantee displacement while ion and electronics, promotes the performance of battery performance.For example, being coupled
Conductive subchannel and diversion subchannel, the ion and electronics simultaneous transmission that will be generated by anode come out to cathode, and by cathode
It is transmitted back to anode, constitutes complete charging and discharging circuit.
In embodiment of the present invention, the carbon material is to have largely as conductive component, basic physicochemical characteristic
The charged particle that can move freely, under the action of an external electric field, carrier makees directed movement, forms apparent electric current.Optionally, institute
Stating carbon material includes pure phase carbon material or the carbon material containing doped chemical.Specifically, the form of the carbon material is unlimited, can be with
For zero-dimension structural such as fullerene, one-dimentional structure such as carbon nanotube, carbon fiber；Two-dimensional structure such as graphene, graphite alkene；And powder
Etc. irregular pattern, such as active carbon, porous carbon.The doped chemical include O, N, B, F, Cl, Co, Fe, Mn, Ni, Au, Cu,
One of Zn, Al, Mg, Pt, Pd, La, Cr, Ge, Pb, Se, Ag, W, Ti, P and Zr or a variety of.
In embodiment of the present invention, the fast-ionic conductor is also known as superionic conductors or solid electrolyte, as diversion
Component, basic physicochemical characteristic are that have high ionic conductivity (10 within the scope of certain temperature-1-10-4S/cm),
Insignificant electronic conductivity (< 10-6S/cm), low ionic conductance activation energy (≤0.30eV), single ionic conductor and ion
Transport number tion≈1.Specifically, the fast-ionic conductor can be oxide type solid electrolyte, sulfide type solid electrolyte,
It can also be the other materials component for meeting the basic physicochemical characteristic of solid electrolyte.Optionally, the oxide type solid-state electricity
Solving matter includes crystalline state Ca-Ti ore type solid electrolyte, crystalline state NASICON type solid electrolyte, crystalline state LISICON type solid state electrolysis
One of matter, Garnet-type solid electrolyte, glassy oxide solid electrolyte are a variety of.Specifically, the oxide
Type solid electrolyte includes but are not limited to Li3PO4,Li2O,Li6BaLa2Ta2O12,Li7La3Zr2O12,Li5La3Nb2O12,
Li5La3M2O12(M=Nb, Ta), Li7+xAxLa3-xZr2O12(A=Zn), Li3Zr2Si2PO12,Li5ZrP3O12,Li5TiP3O12,
Li3Fe2P3O12,Li4NbP3O12, Li1.3Al0.3Ti1.7(PO4)3Deng.The sulfide type solid electrolyte includes crystalline state sulfide
One of type solid electrolyte, glassy state sulfide type solid electrolyte are a variety of.Wherein, the crystalline state sulfide type solid-state
Electrolyte includes but are not limited to Li9.54Si1.74P1.44S11.7Cl0.3, the glassy state type sulfide solid electrolyte includes but not
It is only limitted to GeS2,GeS2,Ga2S3,PS,SiS2,BS,Li2S etc..In embodiment of the present invention, fast-ionic conductor can be in electrolyte
The channel of quickly conduction ion (such as lithium ion) is built between electrode active material, promotes electrode reaction dynamics.
In embodiment of the present invention, the carbon material and the fast-ionic conductor pass through formation of chemical bond strong interaction,
The chemical bond includes at least one of covalent bond, metallic bond, ionic bond.Wherein, when the carbon material is pure phase carbon material
When, the chemical bond includes X-C key, one of Y-C key or a variety of, when the carbon material is the carbon material containing doped chemical
When, the chemical bond includes X-C key, Y-C key, X-Z key, one of Y-Z key or a variety of, wherein X is more than or equal to for electronegativity
The element of carbon, Y are metal or metalloid element, and Z is the doped chemical in the carbon material containing doped chemical.Specifically,
The X includes one of C, N, O, S, B, F, Cl, Br, I, Se or a variety of, the Y include Li, Na, K, Mg, Ca, Al, In,
One of Pb, V, Cr, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, Si, Ga, Sn, Ti, V, Zn, Zr, Ge or a variety of, the Z
Including O, N, B, F, Cl, Co, Fe, Mn, Ni, Au, Cu, Zn, Al, Mg, Pt, Pd, La, Cr, Ge, Pb, Se, Ag, W, Ti, P and Zr
One of or it is a variety of.As shown in Fig. 2, forming X-C key, the schematic diagram of Y-C key for graphene and fast-ionic conductor.
Since conductive component carbon material is relative to fast-ionic conductor, lighter weight, volume be larger, large specific surface area, and big
Specific surface area interface that it can be made to be formed between electrolyte it is more, lead to the consumption and other side reactions of electrolyte
Generation, thus in order to make the conductive sub- composite material of diversion be preferably applied for battery and promote battery performance, synthesis is examined
Consider the relationship between the quality, volume, specific surface area of the carbon material and the fast-ionic conductor, in embodiment of the present invention,
The carbon material quality is accounted for into the Ratio control of the sub- composite material gross mass of the conductive diversion in 0.1%-70%.Specifically,
The carbon material can be the 2%-10% or 20%-30% or 50%- for accounting for the sub- composite material gross mass of the conductive diversion
60%.
The sub- composite material of conductive diversion of the above-mentioned offer of the embodiment of the present invention, is provided simultaneously with high electronics conduction and macroion passes
Performance, and stable structure are led, the modification of electrode material is applied to, maximizing plays the energy of electrode material itself
Density, and improve the long circulating stability and safety of battery.
Correspondingly, the embodiment of the invention provides a kind of preparation methods of the sub- composite material of conductive diversion, including following three
Kind preparation method:
Mode (one): conductive component is provided and leads ion component, conduction is prepared using the first chemically composited mode and is led
Ion composite material；The conductive component includes carbon material, and the diversion subgroup point includes fast-ionic conductor；In this mode, institute
Stating carbon material is the carbon material containing doped chemical.Carbon material containing doped chemical, have in structure more defects from
And can directly with fast-ionic conductor bonding well.The first chemically composited mode include but is not limited to high-energy ball milling method,
High temperature fusion casting.
Mode (two): providing conductive component, and provides diversion subgroup and divide synthesis material, using the second chemically composited mode
The sub- composite material of conductive diversion is prepared；The conductive component includes carbon material, the carbon material include pure phase carbon material or
Carbon material containing doped chemical；It is heat sink that the second chemically composited mode can be, but not limited to chemical vapour deposition technique, vacuum
Area method, magnetron sputtering method, sol-gal process, microwave process for synthesizing, hydro-thermal method, solvent-thermal method, liquid-phase precipitation method, high-energy ball milling method,
One of high temperature fusion casting, molecular beam epitaxial growth method, laser ablation and chemical etching method are a variety of.
Mode (three): ion component is led in offer, and is provided conductive component and prepared raw material, using the chemically composited mode of third
The sub- composite material of conductive diversion is prepared；The chemically composited mode of third can be, but not limited to chemical vapour deposition technique, true
Empty heat sink area method, magnetron sputtering method, sol-gal process, microwave process for synthesizing, hydro-thermal method, solvent-thermal method, liquid-phase precipitation method, high energy ball
One of mill method, high temperature fusion casting, molecular beam epitaxial growth method, laser ablation and chemical etching method are a variety of.Work as conduction
When group is divided into carbon material, it includes carbon source that the conductive component, which prepares raw material, or including carbon source and doped chemical source.
The sub- composite material of conductive diversion that the above method of the embodiment of the present invention is prepared, including conductive component and diversion
Component, the conductive component are chemically bound together with the ion component of leading, the sub- composite material of the conduction diversion
There is conductive subchannel and diversion subchannel simultaneously, the conduction subchannel is coupled with the diversion subchannel.
In embodiment of the present invention, the form of the carbon material is unlimited, can be zero-dimension structural such as fullerene, one-dimentional structure
Such as carbon nanotube, carbon fiber；Two-dimensional structure such as graphene, graphite alkene；And the irregular pattern such as powder, such as active carbon, porous
Carbon etc..The doped chemical include O, N, B, F, Cl, Co, Fe, Mn, Ni, Au, Cu, Zn, Al, Mg, Pt, Pd, La, Cr, Ge, Pb,
One of Se, Ag, W, Ti, P and Zr or a variety of.
In embodiment of the present invention, the fast-ionic conductor can be oxide type solid electrolyte, sulfide type solid-state electricity
Xie Zhi can also be the other materials component for meeting the basic physicochemical characteristic of solid electrolyte.Optionally, the oxide type is solid
State electrolyte includes crystalline state Ca-Ti ore type solid electrolyte, crystalline state NASICON type solid electrolyte, crystalline state LISICON type solid-state
One of electrolyte, Garnet-type solid electrolyte, glassy oxide solid electrolyte are a variety of.Specifically, the oxygen
Compound type solid electrolyte includes but are not limited to Li3PO4,Li2O,Li6BaLa2Ta2O12,Li7La3Zr2O12,Li5La3Nb2O12,
Li5La3M2O12(M=Nb, Ta), Li7+xAxLa3-xZr2O12(A=Zn), Li3Zr2Si2PO12,Li5ZrP3O12,Li5TiP3O12,
Li3Fe2P3O12,Li4NbP3O12, Li1.3Al0.3Ti1.7(PO4)3Deng.The sulfide type solid electrolyte includes crystalline state sulfide
One of type solid electrolyte, glassy state type sulfide solid electrolyte are a variety of.Wherein, the crystalline state sulfide type solid-state
Electrolyte includes but are not limited to Li9.54Si1.74P1.44S11.7Cl0.3, the glassy state type sulfide solid electrolyte includes but not
It is only limitted to GeS2,GeS2,Ga2S3,PS,SiS2,BS,Li2S etc..
In embodiment of the present invention, the fast-ionic conductor synthesis material is according to the fast-ionic conductor specifically to be prepared
Depending on constituent.For example, the fast-ionic conductor to acquisition is Li7La3Zr2O12, then synthesis material can be Li2CO3,
La2O3And ZrO (NO3)2·6H2O, the fast-ionic conductor to acquisition are Li1.3Al0.3Ti1.7(PO4)3, then synthesis material can
To be Li (CH3COO)·2H2O、Al(NO3)·9H2O、NH4H2PO4And butyl titanate.
In embodiment of the present invention, make to be formed between the carbon material and the fast-ionic conductor by above-mentioned preparation method
Chemical bond strong interaction, the chemical bond include at least one of covalent bond, metallic bond, ionic bond.Wherein, when the carbon
When material is pure phase carbon material, the chemical bond includes X-C key, one of Y-C key or a variety of, when the carbon material be containing
When the carbon material of doped chemical, the chemical bond includes X-C key, Y-C key, X-Z key, one of Y-Z key or a variety of, wherein X
It is more than or equal to the element of carbon for electronegativity, Y is metal or metalloid element, and Z is in the carbon material containing doped chemical
Doped chemical.Specifically, the X includes one of C, N, O, S, B, F, Cl, Br, I, Se or a variety of, the Y include Li, Na,
K, one in Mg, Ca, Al, In, Pb, V, Cr, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, Si, Ga, Sn, Ti, V, Zn, Zr, Ge
Kind or it is a variety of, the Z include O, N, B, F, Cl, Co, Fe, Mn, Ni, Au, Cu, Zn, Al, Mg, Pt, Pd, La, Cr, Ge, Pb, Se,
One of Ag, W, Ti, P and Zr or a variety of.The carbon material and the fast-ionic conductor can also form other different forms
Or the bonding of different stoicheiometries.
In embodiment of the present invention, the carbon material accounts for the 0.1%-70% of the sub- composite material quality of the conductive diversion.
Further, the carbon material accounts for the 2%-10% or 20%-30% or 50%- of the sub- composite material quality of the conductive diversion
60%.
In embodiment of the present invention, the concrete operations parameter of each specific preparation method is different anti-according to differential responses raw material
Depending on answering system.
The preparation method of the sub- composite material of above-mentioned conductive diversion provided in an embodiment of the present invention, simple process, operability
By force.
The sub- composite material of conductive diversion based on the above-mentioned offer of the embodiment of the present invention, the embodiment of the invention also provides one kind
Modified electrode material, including electrode material, and it is distributed in inside the electrode material or is coated on the electrode material surface
The sub- composite material of conductive diversion, the electrode material includes positive electrode active materials or negative electrode active material.The conduction diversion
Sub- composite material is described in the above embodiment of the present invention, and details are not described herein again.
Wherein, the conductive sub- composite material of diversion has high ionic conductivity and highly electron conductive simultaneously, is conducive to
The quick transmission of ion and electronics in electrode material improves electrode material kinetics.
In order to which the conduction for enabling the sub- composite material of conductive diversion to improve electrode material well leads ionic nature, while not
The performance for influencing electrode material capacity in embodiment of the present invention, the quality of the sub- composite material of the conductive diversion is accounted for described
The Ratio control of modified electrode material quality is in 0.01%-30%.Further, the matter of the sub- composite material of the conductive diversion
Amount accounts for the 0.1%-1% or 2%-10% or 15%-25% or 5%-20% of the modified pole quality of materials.
In embodiment of the present invention, the electrode material can be different levels structure, the electrode material of different size, tool
Body can be block materials, primary particle or second particle.As shown in figure 3, figure 4 and figure 5, conductive diversion is respectively indicated
Composite material is distributed in the inside of the block materials, is perhaps coated on the primary particle surface or is coated on described two
The structural schematic diagram of secondary particle surface, in figure, 1 is electrode material, and 4 be the sub- composite material of conductive diversion.
In embodiment of the present invention, the specific type of the positive electrode active materials or negative electrode active material is unlimited, optionally,
The positive electrode active materials include LiFePO 4 material, cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, nickel
Cobalt lithium aluminate, nickel ion doped, rich lithium class positive electrode, iron manganese phosphate for lithium, sulphur, sulfur compound, ferric sulfate lithium, lithium fluophosphate, fluorine
One of phosphoric acid vanadium lithium, fluorophosphoric acid iron lithium are a variety of.Optionally, the negative electrode active material include graphite, hard carbon, silicon, germanium,
One of tin, stannic oxide, antimony oxide, antimony carbon composite, tin antimony composite material, lithium titanate are a variety of.
In embodiment of the present invention, the conduction sub- composite material of diversion is formed simultaneously in the modified electrode material is led
Electron channel and diversion subchannel, so that building forms three-dimensional conductive diversion sub-network.The three-dimensional conductive diversion sub-network is continuous
Perforation will be substantially reduced the ionic resistance and electronic impedance of electrode, reduce battery-heating, promote battery heat dissipation, improve battery peace
Total stability.
In embodiment of the present invention, the conduction sub- composite material of diversion is due to having strong bond cooperation between two constituents
With, thus there is structure-integrated, performance continuous-stable advantage, it not will receive the structures such as electrode material expansion, deformation, removing
The influence of variation, when electrode material itself destroys, the conductive sub- composite material of diversion is still able to maintain the ion and electricity of perforation
Sub- transmission characteristic ensures that the chemical property of battery material plays.As shown in fig. 6, being the modified electrode material of the embodiment of the present invention
Expect that the surface composition after deformation occurs in electrode material itself changes schematic diagram.In figure, 1 is electrode material, and 4 be conductive diversion
Composite material；Shown in figure, when electrode material deformation occurs cause structure to be destroyed when, due to conduction and lead ionic material and led to
Chemical bond is crossed as a kind of composite material, even if the composite material by electrode material swelling stress and deformation occurs,
It the conduction of body and leads ion component and still exists simultaneously, so contacting it with electrode material in the sub- composite material of conductive diversion
Place, still keep the complete conductive and sub- binary channels of diversion, and effective guarantee electronics and ion while transmits, to improve
The stability that chemical property plays.And can be known by the prior art of Fig. 1, when shape occurs in electrode material charge and discharge process
When change, due to not interacting point between the conduction and diversion subgroup of prior art electrode material, it will be occurred by stress
Separation, in place of with electrode material contacts, only conductive component, or only lead ion component, and conductive and diversion subgroup point it
Between do not penetrate through, transmission while cannot ensureing electronics and ion, to affect the chemical property of battery.
The modified electrode material of the above-mentioned offer of the embodiment of the present invention is provided simultaneously with high electronics conduction and high ion-conductivity
Can, and conductive diversion sub-network structure is stablized, maximizing plays the energy density of bulk electrode material, extends electronic product
Cruise duration；Its Low ESR will also reduce battery-heating, be conducive to battery long circulating stability, promote the service life of electronic product
And safety, to improve electronic product whole competitiveness.
Correspondingly, the embodiment of the invention also provides a kind of preparation methods of modified electrode material, comprising the following steps:
It takes electrode material synthesis material or directly takes electrode material, and conductive diversion for taking the embodiment of the present invention above-mentioned
Composite material, is prepared modified electrode material by the way of physical blending or chemical crosslinking, and the electrode material includes just
Pole active material or negative electrode active material.
In embodiment of the present invention, the mode of the physical blending or chemical crosslinking includes solution-deposition method, vapor deposition
Method, vacuum heat deposition method, magnetron sputtering method, sol-gal process, microwave process for synthesizing, hydro-thermal method, solvent-thermal method, high-temperature sintering process,
One of high-energy ball milling method is a variety of.It can be dry method, be also possible to wet process.The concrete operations parameter of each method is not according to
Same reaction raw materials, depending on differential responses system.
In embodiment of the present invention, the electrode material can be the electrode material of different levels structure, specifically can be
Block materials, primary particle or second particle.The conduction sub- composite material of diversion is distributed in the inside of the block materials, or
Person is coated on the primary particle surface, or is coated on the second particle surface.
In embodiment of the present invention, the specific type of the positive electrode active materials or negative electrode active material is unlimited, optionally,
The positive electrode active materials include LiFePO 4 material, cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, nickel
Cobalt lithium aluminate, nickel ion doped, rich lithium class positive electrode, iron manganese phosphate for lithium, sulphur, sulfur compound, ferric sulfate lithium, lithium fluophosphate, fluorine
One of phosphoric acid vanadium lithium, fluorophosphoric acid iron lithium are a variety of.Optionally, the negative electrode active material include graphite, hard carbon, silicon, germanium,
One of tin, stannic oxide, antimony oxide, antimony carbon composite, tin antimony composite material, lithium titanate are a variety of.
In embodiment of the present invention, depending on the electrode material synthesis material is specifically formed according to electrode material.For example,
If final electrode material is lithium cobaltate cathode active material, electrode material synthesis material be can be including LiNO3·6H2O, Co
(NO3)2·6H2O and KOH.
In addition, the embodiment of the invention also provides a kind of energy storage device, including anode, cathode, diaphragm and electrolyte, it is described
The positive and/or described cathode includes the above-mentioned modified electrode material of the embodiment of the present invention, in the energy storage device charge and discharge process
In, there is the continuous conductive subchannel of perforation between the electrode material of the modified electrode material and the sub- composite material of conductive diversion
With diversion subchannel, the conduction subchannel and the diversion subchannel composition that is coupled are continuously turned on circuit.Since conduction is led
The conductive component of ion composite material and the strong interaction between ion component with chemical bond is led, therefore even if in electrode material
In the case that structure generates variation, conductive subchannel and diversion subchannel still are able to be coupled parallel appearance, therefore, Neng Gouyou
Effect is transmitted while ensureing electronics and ion, keeps the transmission of inside battery electronics and ion to be in equilibrium state, to be promoted
The stability that battery performance plays avoids Part way from destroying the Local enrichment for leading to electronics or ion and influence electrification
It learns performance to play, leads to the problem of internal resistance of cell increases, heat dissipation is obstructed, battery temperature increases suddenly, brings security risk.
The energy storage device of the embodiment of the present invention can be lithium ion battery, sodium-ion battery, Magnesium ion battery, aluminium ion electricity
Pond or supercapacitor.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.
Embodiment 1
The present embodiment provides a kind of carbon nanotube/Li1.3Al0.3Ti1.7(PO4)3(LATP) the sub- composite material of conductive diversion is used
In positive cobalt acid lithium block materials inter-modification, and the method for being assembled into lithium ion secondary battery:
(1) the sub- composite material of conductive diversion: carbon nanotube/LATP composite material preparation
It takes business single-walled carbon nanotube to disperse solution (solid content 2%) 100mL, sequentially adds final concentration of 0.26mol/L
Lithium acetate (Li (CH3COO)·2H2O), the aluminum nitrate (Al (NO of final concentration of 0.6mol/L3)·9H2O) and final concentration of
Ammonium dihydrogen phosphate (the NH of 0.6mol/L4H2PO4), magnetic agitation obtains mixing salt solution to being completely dissolved under room temperature.Then exist
5mL acetylacetone,2,4-pentanedione is added in the mixing salt solution, stirs 15min, instills the 0.34mol/L metatitanic acid fourth of stoichiometric ratio dropwise
Ester continues to stir 2h obtaining carbon nanotube-LATP colloidal sol, stands curing for 24 hours to get arriving carbon nanotube/LATP composite material.
(2) carbon nanotube/LATP composite modification anode cobalt acid lithium block materials preparation
Carbon nanotube/LATP colloidal sol the 20mL for taking step (1) to prepare is well-dispersed in 200mL aqueous solution, and 2h is stirred by ultrasonic
To being uniformly dispersed, carbon nanotube/LATP sol solution is obtained.Take 1.85g LiNO3·6H2O, 2.9g Co (NO3)2·6H2O
It is dissolved in carbon nanotube/LATP sol solution, then instills 1.5mol/LKOH 5mL dropwise, stirs 30min, it is heavy to obtain black
Obtained black precipitate is washed repeatedly with deionized water, is dried at 80 DEG C, mortar grinder obtains cobalt acid lithium forerunner by starch
Body；Then the cobalt acid lithium presoma is sintered 10h at 700 DEG C, obtains the modified lithium cobaltate cathode material of carbon nanotube/LATP
Material, the carbon nanotube/LATP composite material are distributed in positive cobalt acid lithium material bulk inner.
(3) preparation of lithium ion secondary battery
The carbon nanotube being prepared using step (2)/LATP modified lithium cobaltate cathode material, with conductive agent Super
P, binder PVDF is scattered in nmp solvent according to mass ratio 97:1.5:1.5, stirs evenly, obtain electrode slurry.By gained electricity
Pole slurry is coated in aluminium foil surface, and 100 DEG C of drying obtain anode electrode piece.Cooperate lithium an- ode, electrolyte 1mol/
LLiPF6/ EC+PC+DEC+EMC (volume ratio 1:0.3:1:1), diaphragm is PP/PE/PP three-layer membrane, with a thickness of 15 μm, production
Full battery performance at the soft-package battery of 3.5Ah or so, for test material.
Embodiment 2
The present embodiment provides a kind of graphene/Li7La3Zr2O12(LLZO) the sub- composite material of conductive diversion is used for ternary NCM
Positive electrode second particle cladding, and the method for being assembled into lithium ion secondary battery:
(1) the sub- composite material of conductive diversion: graphene/LLZO composite material preparation
Take Li2CO3, La2O3And ZrO (NO3)2·6H2O is starting material, feeds intake and dissolves according to mol ratio 7.7:3:2
In aqueous citric acid solution (adjustment PH~2), electrolyte salt solution is obtained；Take commercialization graphene oxide water solution (solid content
~4%), according to graphene (solid content): the stoichiometric ratio of LLZO=1wt%, admixed graphite alkene solution and electrolytic salt are molten
Liquid, and PH~5 is adjusted, the oxygen-containing group bonding that abundant back flow reaction 2h, LLZO are rich in graphene surface at 80 DEG C is simultaneously nucleated
Growth forms graphene/LLZO composite material.
(2) graphene/LLZO composite modification NCM positive electrode second particle preparation
Graphene/LLZO composite material that commercialization NMC positive electrode second particle is obtained with step (2) is according to quality
It is sufficiently mixed than 1:99,13Hz ball milling 2h, 5h is sintered at 750 DEG C, form graphene/LLZO composite modification NMC anode
Material.
(3) preparation of lithium ion secondary battery
The graphene being prepared using step (2)/LLZO modified NCM is positive electrode, with conductive agent carbon black, bonding
Agent PVDF is scattered in nmp solvent according to mass ratio 95:2.5:2.5, stirs evenly, obtain electrode slurry.By the electrode obtained slurry
It is coated in aluminium foil surface, 120 DEG C of drying obtain anode electrode piece.Cooperate lithium an- ode, electrolyte 1mol/LLiPF6/EC
+ PC+DEC+EMC (volume ratio 1:0.3:1:1), diaphragm are fabricated to 3Ah or so for PP/PE/PP three-layer membrane with a thickness of 16 μm
Soft-package battery, the full battery performance for test material.
Embodiment 3
The present embodiment provides a kind of carbon-Li1.3Al0.3Ti1.7(PO4)3(LATP) the sub- composite material of conductive diversion is used for silicon-carbon
Cathode primary particle cladding, and the method for being assembled into secondary cell:
(1) the sub- composite material of conductive diversion: carbon/LATP composite material preparation
Pore-creating template polyacrylic resin PAA0.1g is dissolved completely in 50mL ethylene glycol monomethyl ether CH3OCH2CH2In CH,
0.13mol/L lithium acetate (Li (CH is sequentially added according to stoichiometric ratio3COO)·2H2O), 0.3mol/L aluminum nitrate (Al
(NO3)·9H2) and 0.3mol/L ammonium dihydrogen phosphate (NH O4H2PO4), magnetic agitation is to being completely dissolved under room temperature.It is molten in salt-mixture
After 2mL acetylacetone,2,4-pentanedione is added in liquid, 5min is stirred, the 0.17mol/L butyl titanate of stoichiometric ratio is instilled dropwise, continues to stir
Obtain colloidal sol.Colloidal sol is placed at 380 DEG C and heats 20min, obtains LATP xerogel.It will be sieved after xerogel ball milling 30min
(270 mesh), calcines 2h under 900 DEG C of air atmospheres, and furnace cooling obtains porous LATP powder.Weigh the 50g porous LATP powder
End is placed in crucible, imports tube furnace.In N2Under protective atmosphere, be warming up to 700 DEG C according to 5 DEG C/min rate, introduce 3% methane/
Ar gaseous mixture is naturally cooling to room temperature after reacting 1h, obtains the porous LATP composite material with conductive carbon coating.
(2) carbon/LATP composite modification silicon-carbon cathode primary particle preparation
Carbon/LATP composite material that the primary particle for being commercialized silicon-carbon cathode and step (1) are obtained is according to mass ratio 10:
90 are sufficiently mixed, 30Hz ball milling 2h, are sintered 7h at 800 DEG C, carbon/LATP composite material solid phase is coated on silicon-carbon primary particle table
Face, primary particle high temperature sintering, granulation form second particle, that is, form carbon/primary of LATP composite modification silicon-carbon cathode
Grain negative electrode material.
(3) preparation of lithium ion secondary battery
The modified silicon carbon material of the LATP/ carbon being prepared using step (2) does cathode, with conductive agent carbon black, binder
SBR is scattered in aqueous solution according to mass ratio 95:2.5:2.5, stirs evenly, obtain electrode slurry.By the electrode obtained slurry in copper
Foil surface coating, 120 DEG C of drying, obtains negative electricity pole piece.Cooperation commercialization lithium cobaltate cathode piece, electrolyte 1mol/
LLiPF6/ EC+PC+DEC+EMC (volume ratio 1:0.3:1:1), diaphragm is PP/PE/PP three-layer membrane, with a thickness of 18 μm, production
Full battery performance at the soft-package battery of 4Ah or so, for test material.
Embodiment 4
The present embodiment provides a kind of conductive carbon black/Li2S-GeS2The sub- composite wood of (sulfide solid electrolyte) conduction diversion
Material is used for positive LiFePO4 block materials inter-modification, and the method for being assembled into lithium ion secondary battery:
(1) the sub- composite material of conductive diversion: conductive carbon black/Li2S-GeS2The preparation of composite material
Li is prepared using pulse laser deposition on conductive carbon black powder2S-GeS2Sulfide solid electrolyte.It uses
KrF laser (λ=248nm), maintains 5Pa for argon atmosphere, uses Li2S and GeS2For target source, pulse energy is adjusted
200mJ/ pulse, frequency 10Hz, makes Li2S and GeS2Uniform deposition obtains 78Li in conductive carbon black powder surface2S·22GeS2
With conductive carbon black compound.
(2) conductive carbon black/Li2S-GeS2The preparation of composite modification anode LiFePO4 block materials
Conductive carbon black/the Li for taking step (1) to prepare2S-GeS2Compound 10g is uniformly mixed with LiFePO 4 powder 100g
Afterwards, mixing is placed at 750 DEG C and is sintered 6h, obtains conductive carbon black/Li by 30hz ball milling 2h2S-GeS2Modified iron phosphate lithium positive pole
Material, the conductive carbon black/Li2S-GeS2Composite material is distributed in positive LiFePO 4 material bulk inner.
(3) preparation of lithium ion secondary battery
Conductive carbon black/the Li being prepared using step (2)2S-GeS2Modified lithium iron phosphate positive material, with conductive agent
SuperP, binder PVDF are scattered in nmp solvent according to mass ratio 96:2:2, stir evenly, obtain electrode slurry.By gained
Electrode slurry is coated in aluminium foil surface, and 120 DEG C of drying obtain anode electrode piece.Cooperate lithium an- ode, electrolyte 1mol/
LLiPF6/ EC+PC+DEC+EMC (volume ratio 1:0.3:1:1), diaphragm is PP/PE/PP three-layer membrane, with a thickness of 16 μm, production
Full battery performance at the soft-package battery of 4Ah or so, for test material.
Embodiment 5
The present embodiment provides a kind of graphene -75P2S5·20Li2S·5P2O5The diversion of (sulfide solid electrolyte) conduction
Sub- composite material is coated for lithium manganate cathode primary particle, and the method for being assembled into secondary cell:
(1) the sub- composite material of conductive diversion: graphene -75P2S5·20Li2S·5P2O5The preparation of composite material
5g graphene oxide powder, 34.5g P are weighed respectively2S5、44.4g Li2S and 14.2g P2O5As starting material, make
With ball milling 14 hours under high-energy ball milling instrument 500rpm, obtained mixing is heated to 300 DEG C of 6h, graphene oxide is prepared
The 75P of bonding2S5·20Li2S·5P2O5。
(2) graphene/75P2S5·20Li2S·5P2O5The preparation of composite modification anode LiMn2O4 block materials
Graphene/the 75P for taking step (1) to prepare2S5·20Li2S·5P2O5Compound 10g, it is mixed with mangaic acid powder for lithium 100g
After closing uniformly, mixing is placed at 1100 DEG C and is sintered 8h, obtains graphene/75P by 20hz ball milling 2h2S5·20Li2S·5P2O5Change
The manganate cathode material for lithium of property, the graphene/75P2S5·20Li2S·5P2O5Composite material is distributed in positive lithium manganate material
Bulk inner.
(3) preparation of lithium ion secondary battery
Graphene/the 75P being prepared using step (2)2S5·20Li2S·5P2O5Modified manganate cathode material for lithium,
With conductive agent Super P, binder PVDF, it is scattered in nmp solvent according to mass ratio 97:1.5:1.5, stirs evenly, obtains electricity
Pole slurry.The electrode obtained slurry is coated in aluminium foil surface, 100 DEG C of drying obtain anode electrode piece.Cooperate lithium an- ode,
Electrolyte is 1mol/L LiPF6/ EC+PC+DEC+EMC (volume ratio 1:0.3:1:1), diaphragm is PP/PE/PP three-layer membrane, thick
Degree is 14 μm, is fabricated to the soft-package battery of 3.8Ah or so, the full battery performance for test material.
Embodiment 6
The present embodiment provides a kind of graphene/Li1.3Al0.3Ti1.7(PO4)3(LATP) the sub- composite material of conductive diversion, is used for
Positive cobalt acid lithium block materials inter-modification, and the method for being assembled into lithium ion secondary battery:
(1) the sub- composite material of conductive diversion: graphene/LATP composite material preparation
Commercial oxidation graphene dispersion solution (solid content 1%) 100mL is taken, sequentially adds final concentration of 0.13mol/L's
Lithium acetate (Li (CH3COO)·2H2O), the aluminum nitrate (Al (NO of final concentration of 0.3mol/L3)·9H2O) and final concentration of
Ammonium dihydrogen phosphate (the NH of 0.3mol/L4H2PO4), magnetic agitation obtains mixing salt solution to being completely dissolved under room temperature.Then exist
10mL acetylacetone,2,4-pentanedione is added in the mixing salt solution, stirs 30min, instills the 0.17mol/L metatitanic acid of stoichiometric ratio dropwise
Butyl ester continues to stir 4h obtaining graphene-LATP colloidal sol, stands curing for 24 hours to get arriving graphene/LATP composite material.
(2) graphene/LATP composite modification anode cobalt acid lithium block materials preparation
Graphene/LATP colloidal sol the 20mL for taking step (1) to prepare is well-dispersed in 200mL aqueous solution, and ultrasonic agitation 2h is extremely
It is uniformly dispersed, obtains graphene/LATP sol solution.It takes lithium cobaltate cathode material (commercialization powder, China fir China fir 9000E), 5g,
1h is stirred by ultrasonic with graphene/LATP sol solution, stands curing 12h after mixing, is dried at 100 DEG C of gained composite material
Dry, grinding, which is placed at 950 DEG C, is sintered 8h, obtains the modified lithium cobaltate cathode material of graphene/LATP, and the graphene/
LATP composite material is distributed in cobalt acid lithium material block surface.
(3) preparation of lithium ion secondary battery
The modified lithium cobaltate cathode material of the graphene being prepared using step (2)/LATP, with conductive agent Super P,
Binder PVDF is scattered in nmp solvent according to mass ratio 97:1.5:1.5, stirs evenly, obtain electrode slurry.By the electrode obtained
Slurry is coated in aluminium foil surface, and 100 DEG C of drying obtain anode electrode piece.Cooperate lithium an- ode, electrolyte 1mol/
LLiPF6/ EC+PC+DEC+EMC (volume ratio 1:0.3:1:1), diaphragm is PP/PE/PP three-layer membrane, with a thickness of 15 μm, production
Full battery performance at the soft-package battery of 4Ah or so, for test material.
Effect example
To be provided powerful support for technical solution bring beneficial effect of the embodiment of the present invention, provides following performance and survey
Examination.
By no lithium cobaltate cathode material (commercialization powder, China fir China fir using the sub- composite modification of conductive diversion
9000E), with conductive agent Super P, binder PVDF, it is scattered in nmp solvent according to mass ratio 97:1.5:1.5, is stirred evenly,
Obtain electrode slurry.The electrode obtained slurry is coated in aluminium foil surface, 100 DEG C of drying obtain anode electrode piece.Cooperate lithium metal
Cathode, electrolyte are 1mol/L LiPF6/ EC+PC+DEC+EMC (volume ratio 1:0.3:1:1), diaphragm be tri- layers of PP/PE/PP every
Film makes button cell, as a comparison embodiment with a thickness of 15 μm.
Respectively not by the graphene of the embodiment of the present invention 6/LATP modified lithium cobaltate cathode material and comparative example
The lithium cobaltate cathode material being modified carries out Analysis of Surface Topography characterization, and characterization result difference is as shown in Figure 7 and Figure 8, from
It can know in figure, after the sub- composite modification of conductive diversion, the pattern on lithium cobaltate cathode material surface is changed.
Further, the graphene of the embodiment of the present invention 6/LATP modified lithium cobaltate cathode material is subjected to XPS element
It is analyzed and characterized, result is as shown in Figure 9 and Figure 10, the result shows that conductive material graphene (C) and leading ionic material in figure
(Li1.3Al0.3Ti1.7(PO4)3) between the bonding of C-Ti key and the bonding of C-P key has occurred, it was confirmed that conductive material and lead
Bonding occurs between ionic material and forms the sub- composite material of conductive diversion.
Respectively by the battery that the assembling of the embodiment of the present invention 6 obtains and the battery that comparative example assembles, carry out with
Lower battery performance test: using 1C charging/1C electric discharge, charge voltage range 3.0-4.5V tests discharge capacity and head for the first time
Secondary discharging efficiency, the capability value before one-step recording of going forward side by side after 10 circulations, calculates preliminary capacity retention ratio.Test result
It is as shown in table 1:
Table 1
| Serial number | Positive electrode specific capacity | Discharging efficiency for the first time | Recycle preceding 10 circle capacity retention ratio |
| Embodiment 6 | 195mAh/g | 93.5% | 97.2% |
| Comparative example | 187mAh/g | 90.78% | 95.2% |
It can know from the result of table 1, using the electricity of the sub- composite modification of conductive diversion provided in an embodiment of the present invention
The battery of pole material, volumetric properties and cyclical stability all improve, this is because the conductive sub- composite material of diversion is provided simultaneously with
High electronics conduction and high ion-conductivity energy, and stable structure are applied to the modification of electrode material, maximizing hair
The energy density of electrode material itself is waved, and improves the long circulating stability and safety of battery.
Claims (20)
1. a kind of sub- composite material of conduction diversion, which is characterized in that including conductive component and lead ion component, the conductive component
It is chemically bound together with the ion component of leading, the conductive component includes carbon material, and the carbon material includes pure
Phase carbon material or carbon material containing doped chemical, the diversion subgroup point include fast-ionic conductor, and conduction diversion is multiple
Condensation material has conductive subchannel and diversion subchannel simultaneously, and the conduction subchannel is coupled with the diversion subchannel.
2. the sub- composite material of conduction diversion as described in claim 1, which is characterized in that the carbon material includes fullerene, carbon
One of nanotube, carbon fiber, graphene, graphite alkene, active carbon, porous carbon and graphite are a variety of.
3. the sub- composite material of conduction diversion as described in claim 1, which is characterized in that the fast-ionic conductor includes oxide
One of type solid electrolyte, sulfide type solid electrolyte are a variety of.
4. the sub- composite material of conduction diversion as claimed in claim 3, which is characterized in that the oxide type solid electrolyte packet
Include crystalline state Ca-Ti ore type solid electrolyte, crystalline state NASICON type solid electrolyte, crystalline state LISICON type solid electrolyte, pomegranate
One of stone-type solid electrolyte, glassy oxide type solid electrolyte are a variety of；The sulfide type solid electrolyte
Including one of crystalline state sulfide type solid electrolyte, glassy state sulfide type solid electrolyte or a variety of.
5. the sub- composite material of conduction diversion as described in claim 1, which is characterized in that when the carbon material is pure phase carbon material
When, the chemical bond includes X-C key, one of Y-C key or a variety of, when the carbon material is the carbon material containing doped chemical
When, the chemical bond includes X-C key, Y-C key, X-Z key, one of Y-Z key or a variety of, wherein X is more than or equal to for electronegativity
The element of carbon, Y are metal or metalloid element, and Z is the doped chemical in the carbon material containing doped chemical.
6. the sub- composite material of conduction diversion as claimed in claim 5, which is characterized in that the X include C, N, O, S, B, F, Cl,
One of Br, I, Se or a variety of, the Y include Li, Na, K, Mg, Ca, Al, In, Pb, V, Cr, Mn, Fe, Co, Ni, Pd, Pt,
One of Cu, Ag, Au, Si, Ga, Sn, Ti, V, Zn, Zr, Ge or a variety of.
7. conduction diversion sub- composite material as claimed in claim 1 or 5, which is characterized in that the doped chemical include O, N,
B, one of F, Cl, Co, Fe, Mn, Ni, Au, Cu, Zn, Al, Mg, Pt, Pd, La, Cr, Ge, Pb, Se, Ag, W, Ti, P and Zr
Or it is a variety of.
8. the sub- composite material of conduction diversion as described in claim 1, which is characterized in that the conductive component accounts for the conduction and leads
The 0.1%-70% of ion composite material gross mass.
9. a kind of preparation method of the sub- composite material of conduction diversion, which comprises the following steps:
Conductive component is provided and leads ion component, the sub- composite material of conductive diversion is prepared using the first chemically composited mode；
The conductive component includes carbon material, and the carbon material is the carbon material containing doped chemical, and the diversion subgroup point includes fast
Ion conductor；
Or conductive component is provided, and diversion subgroup is provided and divides synthesis material, it is prepared and is led using the second chemically composited mode
Conductance ion composite material；The conductive component includes carbon material, the carbon material include pure phase carbon material or containing doping member
The carbon material of element；
Or provide and lead ion component, and conductive component is provided and prepares raw material, it is prepared and is led using the chemically composited mode of third
Conductance ion composite material；
The conduction sub- composite material of diversion includes conductive component and leads ion component, the conductive component and the diversion subgroup
Dividing and is chemically bound together, the conduction sub- composite material of diversion has conductive subchannel and diversion subchannel simultaneously,
The conduction subchannel is coupled with the diversion subchannel.
10. the preparation method of the sub- composite material of conduction diversion as claimed in claim 9, which is characterized in that first chemistry
Complex method includes high-energy ball milling method, high temperature fusion casting.
11. the preparation method of the sub- composite material of conduction diversion as claimed in claim 9, which is characterized in that second chemistry
Complex method and the chemically composited mode of the third are independently selected from chemical vapour deposition technique, vacuum heat deposition method, magnetron sputtering
Method, microwave process for synthesizing, hydro-thermal method, solvent-thermal method, liquid-phase precipitation method, high-energy ball milling method, high temperature fusion casting, is divided sol-gal process
One of beamlet epitaxial growth method, laser ablation and chemical etching method are a variety of.
12. a kind of modified electrode material, which is characterized in that including electrode material, and be distributed in inside the electrode material or
It is coated on the sub- composite material of conductive diversion of the electrode material surface, the electrode material includes positive electrode active materials or cathode
Active material, the conduction sub- composite material of diversion are the sub- composite material of the described in any item conductive diversions of claim 1-8.
13. modified electrode material as claimed in claim 12, which is characterized in that the quality of the sub- composite material of the conduction diversion
Account for the 0.01%-30% of the modified electrode material gross mass.
14. modified electrode material as claimed in claim 12, which is characterized in that the electrode material includes block materials, and one
Secondary particle or second particle, the conduction sub- composite material of diversion is distributed in the inside of the block materials, or is coated on described
Primary particle or the second particle surface.
15. modified electrode material as claimed in claim 12, which is characterized in that the positive electrode active materials include LiFePO4
Material, cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, nickel ion doped, rich lithium class anode
One of material, iron manganese phosphate for lithium, sulphur, sulfur compound, ferric sulfate lithium, lithium fluophosphate, fluorophosphoric acid vanadium lithium, fluorophosphoric acid iron lithium or
It is a variety of；The negative electrode active material includes graphite, hard carbon, silicon, germanium, tin, stannic oxide, antimony oxide, antimony carbon composite, tin antimony
One of composite material, lithium titanate are a variety of.
16. modified electrode material as claimed in claim 12, which is characterized in that the conduction sub- composite material of diversion is described
Building forms three-dimensional conductive diversion sub-network in modified electrode material.
17. a kind of preparation method of modified electrode material, which comprises the following steps:
It takes electrode material synthesis material or directly takes electrode material, and the described in any item conductions of claim 1-8 such as is taken to lead
Modified electrode material, the electrode material packet is prepared in ion composite material by the way of physical blending or chemical crosslinking
Include positive electrode active materials or negative electrode active material.
18. the preparation method of modified electrode material as claimed in claim 17, which is characterized in that the physical blending or chemistry
The mode of crosslinking includes solution-deposition method, vapour deposition process, vacuum heat deposition method, magnetron sputtering method, sol-gal process, microwave conjunction
One of Cheng Fa, hydro-thermal method, solvent-thermal method, high-temperature sintering process, high-energy ball milling method are a variety of.
19. a kind of energy storage device, including anode, cathode, diaphragm and electrolyte, which is characterized in that described positive and/or described negative
Pole includes such as described in any item modified electrode materials of claim 12-16, described in the energy storage device charge and discharge process
There is the continuous conductive subchannel of perforation and diversion between the electrode material of modified electrode material and the sub- composite material of conductive diversion
Subchannel, the conduction subchannel and the diversion subchannel composition that is coupled are continuously turned on circuit.
20. energy storage device as claimed in claim 19, which is characterized in that the energy storage device include lithium ion battery, sodium from
Sub- battery, Magnesium ion battery, aluminium ion battery or supercapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711009717.2A CN109713235A (en) | 2017-10-25 | 2017-10-25 | A kind of sub- composite material and preparation method of conduction diversion, modified electrode material and energy storage device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711009717.2A CN109713235A (en) | 2017-10-25 | 2017-10-25 | A kind of sub- composite material and preparation method of conduction diversion, modified electrode material and energy storage device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109713235A true CN109713235A (en) | 2019-05-03 |
Family
ID=66252107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711009717.2A Pending CN109713235A (en) | 2017-10-25 | 2017-10-25 | A kind of sub- composite material and preparation method of conduction diversion, modified electrode material and energy storage device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109713235A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110729511A (en) * | 2019-10-28 | 2020-01-24 | 溧阳天目先导电池材料科技有限公司 | Lithium ion solid electrolyte material with composite core-shell structure and preparation method thereof |
| CN110931797A (en) * | 2019-12-09 | 2020-03-27 | 宁波容百新能源科技股份有限公司 | High-nickel positive electrode material with composite coating layer and preparation method thereof |
| CN111029553A (en) * | 2019-12-25 | 2020-04-17 | 溧阳中科海钠科技有限责任公司 | Sodium-ion battery positive electrode material and preparation method and application thereof |
| CN111048756A (en) * | 2019-12-04 | 2020-04-21 | 兰溪致德新能源材料有限公司 | High-conductivity silica negative electrode material and application thereof |
| CN111682200A (en) * | 2020-07-14 | 2020-09-18 | 万华化学集团股份有限公司 | Positive electrode material for lithium ion battery and preparation method thereof |
| CN112018400A (en) * | 2020-08-28 | 2020-12-01 | 华中科技大学 | Fullerene-based Fe and N doped porous carbon material and preparation method and application thereof |
| CN112310394A (en) * | 2019-07-26 | 2021-02-02 | 宝山钢铁股份有限公司 | Solid electrolyte coated battery negative electrode material and preparation method thereof |
| CN113054164A (en) * | 2021-03-17 | 2021-06-29 | 合肥国轩高科动力能源有限公司 | Preparation method of low-internal-resistance ternary single crystal pole piece |
| CN113206249A (en) * | 2021-04-19 | 2021-08-03 | 湖州金灿新能源科技有限公司 | Lithium battery silicon-oxygen composite negative electrode material with good electrochemical performance and preparation method thereof |
| CN113809331A (en) * | 2020-06-17 | 2021-12-17 | 东营市海科新源化工有限责任公司 | Multifunctional additive for lithium ion battery anode, preparation method of multifunctional additive and lithium ion battery |
| CN113964377A (en) * | 2021-09-28 | 2022-01-21 | 安普瑞斯（无锡）有限公司 | Solid electrolyte and preparation method thereof |
| CN114725334A (en) * | 2022-03-10 | 2022-07-08 | 中南大学 | Flower-like zinc selenide-manganese/carbon composite material and preparation method and application thereof |
| WO2023092894A1 (en) * | 2021-11-29 | 2023-06-01 | 蜂巢能源科技股份有限公司 | Hard carbon composite material, and preparation method therefor and use thereof |
| CN116706041A (en) * | 2023-08-03 | 2023-09-05 | 江苏正力新能电池技术有限公司 | Sodium ion positive electrode material and preparation and application thereof |
| CN113964377B (en) * | 2021-09-28 | 2024-04-19 | 安普瑞斯（无锡）有限公司 | Solid electrolyte and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103165885A (en) * | 2011-12-14 | 2013-06-19 | 苏州宝时得电动工具有限公司 | Anode material and anode and battery provided with anode and preparation method of anode material |
| WO2014185494A1 (en) * | 2013-05-16 | 2014-11-20 | 住友大阪セメント株式会社 | Carbon-coated active-material complex and lithium-ion battery |
| CN104332617A (en) * | 2014-09-19 | 2015-02-04 | 青岛乾运高科新材料股份有限公司 | Lithium-rich manganese-based mixed conductor positive electrode material and preparation method thereof |
-
2017
- 2017-10-25 CN CN201711009717.2A patent/CN109713235A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103165885A (en) * | 2011-12-14 | 2013-06-19 | 苏州宝时得电动工具有限公司 | Anode material and anode and battery provided with anode and preparation method of anode material |
| WO2014185494A1 (en) * | 2013-05-16 | 2014-11-20 | 住友大阪セメント株式会社 | Carbon-coated active-material complex and lithium-ion battery |
| CN104332617A (en) * | 2014-09-19 | 2015-02-04 | 青岛乾运高科新材料股份有限公司 | Lithium-rich manganese-based mixed conductor positive electrode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YARUI CHENG: "Enhanced Electrochemical Performance of Li3V2(PO4)3/C Coated with Li Fast Ion Conductive Li7La3Zr2O12", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112310394A (en) * | 2019-07-26 | 2021-02-02 | 宝山钢铁股份有限公司 | Solid electrolyte coated battery negative electrode material and preparation method thereof |
| CN110729511A (en) * | 2019-10-28 | 2020-01-24 | 溧阳天目先导电池材料科技有限公司 | Lithium ion solid electrolyte material with composite core-shell structure and preparation method thereof |
| CN111048756A (en) * | 2019-12-04 | 2020-04-21 | 兰溪致德新能源材料有限公司 | High-conductivity silica negative electrode material and application thereof |
| CN110931797A (en) * | 2019-12-09 | 2020-03-27 | 宁波容百新能源科技股份有限公司 | High-nickel positive electrode material with composite coating layer and preparation method thereof |
| CN111029553A (en) * | 2019-12-25 | 2020-04-17 | 溧阳中科海钠科技有限责任公司 | Sodium-ion battery positive electrode material and preparation method and application thereof |
| CN113809331B (en) * | 2020-06-17 | 2023-06-20 | 东营市海科新源化工有限责任公司 | Multifunctional additive, preparation method thereof and lithium ion battery |
| CN113809331A (en) * | 2020-06-17 | 2021-12-17 | 东营市海科新源化工有限责任公司 | Multifunctional additive for lithium ion battery anode, preparation method of multifunctional additive and lithium ion battery |
| CN111682200A (en) * | 2020-07-14 | 2020-09-18 | 万华化学集团股份有限公司 | Positive electrode material for lithium ion battery and preparation method thereof |
| CN112018400A (en) * | 2020-08-28 | 2020-12-01 | 华中科技大学 | Fullerene-based Fe and N doped porous carbon material and preparation method and application thereof |
| CN113054164A (en) * | 2021-03-17 | 2021-06-29 | 合肥国轩高科动力能源有限公司 | Preparation method of low-internal-resistance ternary single crystal pole piece |
| CN113206249A (en) * | 2021-04-19 | 2021-08-03 | 湖州金灿新能源科技有限公司 | Lithium battery silicon-oxygen composite negative electrode material with good electrochemical performance and preparation method thereof |
| CN113964377A (en) * | 2021-09-28 | 2022-01-21 | 安普瑞斯（无锡）有限公司 | Solid electrolyte and preparation method thereof |
| CN113964377B (en) * | 2021-09-28 | 2024-04-19 | 安普瑞斯（无锡）有限公司 | Solid electrolyte and preparation method thereof |
| WO2023092894A1 (en) * | 2021-11-29 | 2023-06-01 | 蜂巢能源科技股份有限公司 | Hard carbon composite material, and preparation method therefor and use thereof |
| CN114725334A (en) * | 2022-03-10 | 2022-07-08 | 中南大学 | Flower-like zinc selenide-manganese/carbon composite material and preparation method and application thereof |
| CN114725334B (en) * | 2022-03-10 | 2024-02-06 | 湖南金钺新材料有限责任公司 | Flower-like zinc selenide-manganese/carbon composite material and preparation method and application thereof |
| CN116706041A (en) * | 2023-08-03 | 2023-09-05 | 江苏正力新能电池技术有限公司 | Sodium ion positive electrode material and preparation and application thereof |
| CN116706041B (en) * | 2023-08-03 | 2023-10-27 | 江苏正力新能电池技术有限公司 | Sodium ion positive electrode material and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109713235A (en) | A kind of sub- composite material and preparation method of conduction diversion, modified electrode material and energy storage device | |
| Kim et al. | Reversible and high‐capacity nanostructured electrode materials for Li‐ion batteries | |
| US10957903B2 (en) | Layered lithium-rich manganese-based cathode material with olivine structured LIMPO4 surface modification and preparation method thereof | |
| CN100446307C (en) | Method for preparing lithium secondary cell electrode containing nano additive | |
| CN103456936B (en) | Sodium ion secondary battery and the preparation method of layered titanate active substance, electrode material, both positive and negative polarity and active substance | |
| US7887954B2 (en) | Electrochemical composition and associated technology | |
| CN102810669B (en) | The method of positive electrode material for secondary battery and this material of manufacture | |
| Li et al. | Improve first-cycle efficiency and rate performance of layered-layered Li1. 2Mn0. 6Ni0. 2O2 using oxygen stabilizing dopant | |
| CN109244365A (en) | Anode material for lithium-ion batteries and preparation method thereof, anode and lithium ion battery | |
| CN109390622A (en) | Lithium solid state battery | |
| CN101826617B (en) | Preparation method of lithium iron phosphate | |
| CN113707875B (en) | Spinel type lithium nickel manganese oxide, preparation method thereof and lithium ion battery | |
| Yuan et al. | Surfactant-assisted hydrothermal synthesis of V2O5 coated LiNi1/3Co1/3Mn1/3O2 with ideal electrochemical performance | |
| CN108281665A (en) | A kind of method of duplicature protection metal negative electrode | |
| CN101752562B (en) | Compound doped modified lithium ion battery anode material and preparation method thereof | |
| Kim et al. | Preparation and cycle performance at high temperature for Li [Ni 0.5 Co 0.2 Mn 0.3] O 2 coated with LiFePO 4 | |
| CN104009252A (en) | Sodium-ion battery and preparation method thereof | |
| CN102496714A (en) | Anode active substance, production method thereof, and lithium ion battery employing anode active substance | |
| Wu et al. | Synthesis and electrochemical performance of SnO2–Fe2O3 composite as an anode material for Na-ion and Li-ion batteries | |
| CN109037659A (en) | A kind of preparation method of bilayer carbon-coated LiFePO 4 for lithium ion batteries material | |
| CN105684198B (en) | Sode cell positive active material and sode cell | |
| CN102479945B (en) | The preparation method of spherical lithium iron phosphate anode material | |
| CN110400929A (en) | A kind of metal-doped ternary positive electrode active material of Phosphate coating and its preparation and application | |
| CN102544492A (en) | Lithium iron phosphate/graphene composite material with interlay sheet structure and preparation method and application thereof | |
| CN103618065B (en) | LiFePO 4 material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190503 |
|
| RJ01 | Rejection of invention patent application after publication |