CN110165168A - A kind of composite positive pole and its preparation method and application - Google Patents
A kind of composite positive pole and its preparation method and application Download PDFInfo
- Publication number
- CN110165168A CN110165168A CN201910403900.3A CN201910403900A CN110165168A CN 110165168 A CN110165168 A CN 110165168A CN 201910403900 A CN201910403900 A CN 201910403900A CN 110165168 A CN110165168 A CN 110165168A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- nanocrystalline
- positive pole
- rich
- composite positive
- 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.)
- Granted
Links
Classifications
-
- 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
- H01M4/362—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
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 present invention relates to a kind of composite positive poles and its preparation method and application, the composite positive pole includes nanocrystalline positive electrode, be coated on the nanocrystalline positive electrode surface is rich in rock salt defect layer, and the tubular graphene alkene network structure being interconnected to form by three-dimensional grapheme tube covalent bond for nanocrystalline positive electrode of the carrier surface in situ cladding rich in rock salt defect layer；It is LiMO that the nanocrystalline positive electrode, which is chemical composition,2Layered cathode material, M be cobalt, manganese, nickel, ruthenium element at least one；The group rich in rock salt defect layer becomes transition metal oxide or/and lithium salts.
Description
Technical field
The present invention relates to a kind of composite positive poles and its preparation method and application, and in particular to one kind is based on being rich in
The composite positive pole and preparation method thereof of the laminar nano crystalline substance novel high-power application of rock-salt defect layer cladding, belongs to
Field of nanometer material technology and electrochemical energy storing device field.
Background technique
The high-performance storage new material that development breaks through current material limiting performance is to research and develop next-generation high-performance energy storage device
Crucial and important support.Electrode material for lithium ion cell follows body phase energy storage mechanism, relies on lithium ion in electrode material crystal
High energy storage is realized in internal fake capacitance deintercalation reaction, while cannot achieve the height of high speed charge/discharge because bulk diffusion rate limits
Power characteristic；The following application traction, which proposes energy storage device, takes into account high energy storage density, high-specific-power, long-life, high security
Etc. the requirement that is risen to for grade of comprehensive performances, from material structure-performance structure-activity relationship angle, break through existing research level and
Cognitive ability develops new electrode material microstructure and its constructs/control technique, based on new construction realization novel energy-storing/put
Energy mechanism is an important research direction of the high-performance storage new material that development breaks through current material limiting performance.
The LiMO of traditional lithium electricity positive electrode2Stratified material structure, the requirement based on electrochemical stability, the scale of particle
It is very big, up to tens microns.While ensure that stability of material, it is not able to satisfy under the conditions of high rate charge-discharge due to ion
Diffusion length is too long, cannot quickly carry out the problem of lithium ion conduction.By taking lithium cobaltate cathode material as an example, have preferable high
Cryogenic property and high rate performance, but the system is only 4.2V, this is because current LiCoO2It is general only to utilize its theoretical capacity
Half.So high irreversible capacity is mainly and LiCoO2Series of phase transitions during lithium insertion/deintercalation is related.Low
Voltage area, there are insulator-metal phase transitions, and when being charged to 4.2V, about 50% Li ion is deviate from and material is undergone
Order-disorder change from hexagonal structure to monoclinic structure, when charging to 4.5V or more, LiCoO2Experience from the O3 stage to
Another transformation in H1-3 or O6 phase stage.These phase transformations are reversible, but order-disorder change substantially reduces Li+'s
Diffusion coefficient and transformation to transition state generate between mechanical strain and particle/internal micro-crack, lead to deep charge
LiCoO2There is apparent capacity attenuation.Therefore LiCoO at this stage2Charging voltage is limited in 4.2V.Promote LiCoO2Charging cut
Specific energy and specific power can be improved in only voltage, but raising charge cutoff voltage can give LiCoO2Security performance bring hidden danger.For
Holding LiCoO2Structural intergrity and stable chemical property, various improved technologies are come into being, wherein passing through metal member
The means of plain (Mn, Ni etc.) doping achieve better effects (Journal of the Electrochemical Society,
2000,147(9):3183-3189；RSC Advances,2015,5(64):51483-51488；ACS Applied
Materials&Interfaces, 2016,8 (4): 2723-2731, Electrochemistry Communications,
2010,12(11):1524-1526；Nanoscale, 2014,6 (2): 860-866, Nano Research, 2012,5 (6):
395-401；NPG Asia Materials, 2014,6 (9): e126.), by LiCoO2Charging voltage from 4.2V promoted to
4.35V, capacity are also raised to 165mAh/g, however manganese results in initial discharge capacity without electro-chemical activity in charge and discharge process
Reduction；Although Ni2+/Ni4+Redox reaction improve charge/discharge capacity, but Ni2+(r=0.069nm) and Li+ (r
=0.076nm) there are similar particle radii to will lead to cationic mixing, cause chemical property to be deteriorated.It charges after preliminary doping
To 4.4V, initial discharge capacity is close to 180mAh g under 0.1C multiplying power-1, however serious polarization, cyclical stability are poor；By changing
Into LiCo1-x(Ni0.5Mn0.5)xO2Increase of the series with cobalt content, the reduction of lithium nickel mixing degree, chemical property can just improve.
But allow people regrettably this be also far below its theoretical capacity (274mAh/g).
Summary of the invention
In view of the above-mentioned problems, the first object of the present invention is to provide a kind of low cost, electrochemical performance, can advise greatly
The novel composite positive pole towards high power applications of mould production.Second is designed to provide the low cost, electrochemistry
The preparation method for the novel composite positive pole towards high power applications that energy is excellent, can be mass-produced.Third purpose exists
In offer low cost, electrochemical performance, the novel composite positive pole towards high power applications that can be mass-produced
Application in energy storage device field.
On the one hand, the present invention provides a kind of composite positive pole, the composite positive pole includes nanocrystalline positive material
Material is coated on being rich in rich in rock salt defect layer, and for carrier surface in situ cladding for the nanocrystalline positive electrode surface
The tubular graphene alkene net of the nanocrystalline positive electrode of rock salt defect layer being interconnected to form by three-dimensional grapheme tube covalent bond
Network structure；
It is LiMO that the nanocrystalline positive electrode, which is chemical composition,2Layered cathode material, M be cobalt, manganese, nickel, ruthenium element extremely
Few one kind；The group rich in rock salt defect layer becomes transition metal oxide or/and lithium salts, preferably Li2RuO3、RuO2、
Al2O3、IrO2、TiO2, at least one of MgO.
Summarize in the disclosure, is constructed on the surface of nanocrystalline positive electrode (preferably laminated structure nano crystalline substance positive electrode) rich
Containing rock salt (rock-salt) defect layer, i.e., with defect layer (defect and the hole knot of rock salt structure (rock-salt structure)
Structure), it is initially formed core-shell structure, it is same in quickly transmitting for interface to be conducive to lithium ion containing defective and hole configurations defect layer
When, it should also ensure that nanocrystalline positive electrode was isolated with electrolyte formation rich in rock salt (rock-salt) defect layer, and promote electrode
Stability.Moreover, it is compound with three-dimensional grapheme tube progress again, the electronic conductivity of electrode material can also be further promoted, and
The tubular graphene alkene network structure that three-dimensional grapheme tube covalent bond is interconnected to form improves positive electrode itself closs packing knot
Structure is finally obtained with height ratio capacity, high voltage, the novel composite electrode material of long-life.
Preferably, the size of the nanocrystalline positive electrode is 20~200nm, and internal with 1nm or less atom
The minimum micropore tridimensional structure of cluster scale size.
Preferably, it is described rich in rock salt defect layer with a thickness of 1~10nm.
Preferably, the number of plies of graphene is 1~10 layer, 50~300nm of caliber in tube wall in the three-dimensional grapheme tube, pipe
It is 1~20 μm long, the content 99wt.% or more of C in grapheme tube.
Preferably, the tubular graphene alkene network structure accounts for the 0.1%~10% of composite positive pole gross mass.
On the other hand, the present invention also provides a kind of preparation methods according to above-mentioned composite positive pole, comprising:
(1) at least one of transition metal oxide, lithium salts and nanocrystalline positive electrode material precursor are chosen as raw material, then is passed through
Ball milling mixing is carried out, obtains being coated with the nanocrystalline positive electrode material precursor rich in rock salt defect layer, the nanocrystalline positive material
Material precursor is Li2CO3With the carbonate of M；
(2) the nanocrystalline positive electrode material precursor that will be enriched in rock salt defect layer is supported in situ in three-dimensional grapheme tube structure, so
Afterwards in the mixed atmosphere containing inert gas and hydrogen, calcination process is carried out at 400~1000 DEG C, obtains the anode composite
Material.
In the disclosure, choose rich in rock salt defect layer raw material (at least one of transition metal oxide, lithium salts) and
Nanocrystalline positive electrode material precursor (Li2CO3With the carbonate of M) ball milling mixing is carried out, it obtains being coated with rich in rock salt defect layer
Nanocrystalline positive electrode material precursor.By it again with three-dimensional grapheme after mixing, in the mixing containing inert gas and hydrogen
In atmosphere, calcination process is carried out at 400~1000 DEG C.Firstly, in above-mentioned roasting process, in such a way that hydrogen portion restores
It prepares containing defective and hole configurations rich in rock salt defect layer, and nanocrystalline due to being further suppressed rich in rock salt defect layer
Positive electrode is grown up, and the capacitance characteristic of composite positive pole is improved, and improves the high magnification electrochemistry of composite positive pole
Energy.Secondly, in above-mentioned roasting process, covalent bond is interconnected to form between three-dimensional grapheme tube tubular graphene alkene network knot
Structure also improves positive electrode electronic conductivity and close-packed structure.Third, during above-mentioned burnt, nanocrystalline positive electrode
It is carried in situ while formation in tubular graphene alkene network structure.In conclusion finally obtaining with height ratio capacity, high electricity
Pressure, the novel composite electrode material of long-life.
Preferably, the ball milling mixing is wet ball grinding, parameter includes: that ratio of grinding media to material is (10~35): 1；Solvent is water, second
The mass ratio of at least one of alcohol, acetone, solvent and raw material is (0~1): 1；Rotational speed of ball-mill is 100~10000 revs/min,
Ball-milling Time is 0.5~12h.
Preferably, the time of the roasting is 0.5~12 hour.
Preferably, the pressure of the mixed atmosphere is 0.5~5 atmospheric pressure.
Preferably, the percent by volume of inert gas and hydrogen is (0.05~0.95) in the mixed atmosphere: 1, it is described
Inert atmosphere is at least one of argon gas and nitrogen.
In another aspect, the present invention also provides a kind of above-mentioned composite positive poles to prepare answering in high power accumulator
With.
The utility model has the advantages that
The invention discloses a kind of low cost, electrochemical performance, can be mass-produced it is novel towards high power applications
Composite positive pole and preparation method thereof, composite positive pole have height ratio capacity (>=250mAh/g), high voltage (>=
4.5V), the electrochemical energy storages characteristic such as long-life (50,000 circulation@80%DOD).And the preparation method simple process, process are easily-controllable
System, equipment investment is few, can be mass produced.It can be applied to energy storage device field.
Detailed description of the invention
Fig. 1 is the structure composition schematic diagram of the composite positive pole prepared in the present invention；
Fig. 2 be cobalt acid lithium prepared by embodiment 1 it is nanocrystalline/micron order for preparing of grapheme tube composite positive pole and comparative example 1
The chemical property of lithium cobaltate cathode material.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
A kind of height ratio capacity is provided in the present invention, high voltage, long-life, the novel high-power that can be mass-produced are answered
Composite positive pole, comprising: nanocrystalline positive electrode, be coated on nanocrystalline positive electrode surface is rich in rock-salt
Defect layer (the two formed surface be coated with the nanocrystalline positive electrode rich in rock-salt defect layer) and in situ negative
The highly conductive tubular graphene alkene network of above-mentioned composite material constructed by three-dimensional grapheme tube is carried, structure is as shown in Figure 1.Its
In, surface is coated with nanocrystalline positive electrode in the nanocrystalline positive electrode rich in rock-salt defect layer and receives for layer structure
Meter Jing, size 20-200nm, inside have the minimum micropore tridimensional structure of 1nm or less elementide scale.It is nanocrystalline
Positive electrode can be LiMO2Layered cathode material, M be cobalt, manganese, nickel, ruthenium element one or more.
In alternate embodiments, the main component rich in rock-salt defect layer is Li2RuO3、RuO2、Al2O3、
IrO2、TiO2, one or more of transition metal oxides and the lithium salts composition such as MgO, account for composite positive pole gross mass
0.0001%-1%.Thickness rich in rock-salt defect layer can be 1-10nm.
In alternate embodiments, covalent bond highly conductive tubular graphene alkene net interconnected between three-dimensional grapheme tube
Network.The number of plies of graphene is 1-10 layers, caliber 50-300nm, 1-20 μm of pipe range in the tube wall of grapheme tube, C in grapheme tube
Content 99wt.% or more.
In an embodiment of the present invention, based on the laminar nano rich in rock-salt defect layer cladding it is brilliant it is compound just
The preparation method simple process of pole material, process is easy to control, and electrochemical performance, preparation cost is low, is suitable for energy storage device
Field.Illustrate to following exemplary the preparation method of composite positive pole provided by the invention.
It chooses nanocrystalline positive electrode material precursor and the mixing of one or more of transition metal oxide and lithium salts is equal
It is even, it obtains to surface and is coated with the nanocrystalline positive electrode material precursor rich in rock salt defect layer.Wherein, transition metal oxide and lithium
The mass ratio of salt gross mass and nanocrystalline positive electrode material precursor can be 1:(0.0001%-1%).It is described it is uniformly mixed be to adopt
With wet ball grinding, ratio of grinding media to material is (10~35): 1；The solvent added when ball milling is one of water, ethyl alcohol, acetone etc. or two
Kind or more mixing, the mass ratio of solvent and mixing material is (0~1): 1；Rotational speed of ball-mill is 100-10000 revs/min, ball milling
Time is 0.5~12h.
Surface is coated with the nanocrystalline positive electrode material precursor rich in rock salt defect layer and loads to three-dimensional grapheme tube in situ
In structure, the mass ratio of the additional amount and composite positive pole that control three-dimensional grapheme tube is (0.001~0.1): 1.
Then high-temperature roasting is handled under the mixed atmosphere of inert gas/hydrogen, and moderately reduction generation lacks in roasting process
It falls into, forms composite positive pole.Wherein inert atmosphere can be argon gas and nitrogen etc..The temperature of the roasting can for 400~
1000℃.The time of roasting can be 0.5~12h.The percent by volume of inert gas and hydrogen is (0.05 in the mixed atmosphere
~0.95): 1.Air pressure can be 0.5~5 atmospheric pressure when the ventilation work of mixed atmosphere.
It should be noted that nanocrystalline positive electrode material precursor is using sol-gel, ball-milling method or coprecipitation etc. in the present invention
Preparation.Nanocrystalline positive electrode material precursor used is that one or more mix in the hydrochloride of lithium carbonate and M.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
(1) by Li2CO3(74g) and CoCO3(119g) is 1 progress ball-milling method mixing according to Li/Co molar ratio, is added a small amount of
Al2O3(0.18g)、RuO2(0.35g) carries out wet ball grinding, ratio of grinding media to material 25:1, solvent and mixing material in ethanol solution
Mass ratio be 0.5:1, rotational speed of ball-mill be 1000 revs/min, Ball-milling Time be 5 hours；
(2) compound (mixing) is carried out with three-dimensional grapheme tube again, ratio of the three-dimensional grapheme tube in composite positive pole is
5wt%, grapheme tube caliber be 100nm, pipe range be 5 μm, the content 99.0wt.% of C, graphene be averaged the number of plies be 5 layers.In argon
Lower 600 DEG C of gas atmosphere, normal pressure are sintered 10 hours, and the composite positive pole of preparation (cobalt acid lithium is nanocrystalline/grapheme tube anode composite
Material).The average-size of nanocrystalline positive electrode is 150nm in gained composite positive pole, and inside has the atom of 1nm or so
The minimum microcellular structure of cluster scale.Its thickness rich in rock-salt defect layer is about 5nm, main component be aluminium oxide and
Ruthenium-oxide.Half-cell is prepared based on gained composite positive pole, show through electrochemical property test: charging voltage is reachable
4.5V shows the specific capacity of 250mAh/g under the conditions of 0.5C multiplying power；Battery is still able to maintain 84% ratio under 6C multiplying power
Capacity shows excellent high rate performance (as shown in Figure 2).In addition, battery depth of discharge be 80% under conditions of, it can be achieved that
50000 circulations, capacity retention ratio are greater than 70%.
By comparison, it was found that improving the capacitance characteristic of positive electrode by reducing the size of composite positive pole, changing
While the high magnification chemical property of kind positive electrode, by forming nucleocapsid knot in its surface construction rock-salt defect layer
Structure, the quick transmission conducive to lithium ion at interface, while boundary layer guarantee to be isolated in positive electrode and electrolyte, and it is steady to promote electrode
It is qualitative.Compound, the close-packed structure of promotion electrode material electronic conductivity and positive electrode, benefit are carried out with three-dimensional grapheme tube
In the promotion of the height ratio capacity of positive electrode, high voltage, long-life performance.
Embodiment 2
(1) by Li2CO3(74g)、CoCO3(95.1g) and NiCO3(23.7g) is 1 progress ball milling according to Li/ (Co+Ni) molar ratio
Method mixing, wherein the molar ratio of Co and Ni is 4:1, and a small amount of Li is added2RuO3(0.01g)、IrO2(0.02g), MgO (0.03g) material
Material, carries out wet ball grinding in acetone soln, ratio of grinding media to material 32:1, and the mass ratio of solvent and mixing material is 0.7:1, and ball milling turns
3000 revs/min of speed, Ball-milling Time are 2 hours；
(2) compound with three-dimensional grapheme tube progress again, ratio of the three-dimensional grapheme tube in composite positive pole is 7wt%, stone
Black alkene pipe caliber be 200nm, pipe range be 3 μm, the content 99.3wt.% of C, graphene be averaged the number of plies be 3 layers.In 5% hydrogen and
Lower 800 DEG C of argon gas mixed atmosphere, 1.2 atmospheric pressure are sintered 10 hours, the composite positive pole of preparation.Gained composite positive pole
In the average-size of nanocrystalline positive electrode be 120nm, inside has the minimum micropore knot of the elementide scale of 1nm or so
Structure.It wherein, is about 3nm, main component Li rich in rock-salt defect layer thickness2RuO3、IrO2,MgO.Gained anode composite
Material assembles half-cell, and show through electrochemical property test: charging voltage is up to 4.5V；Under the conditions of 0.5C multiplying power, show
The specific capacity of 280mAh/g；Battery is still able to maintain 89% specific capacity under 6C multiplying power；The item that battery is 80% in depth of discharge
, it can be achieved that 50,000 circulations, capacity retention ratio are greater than 75% under part.
Embodiment 3
In example 2 by Li2CO3(74g)、CoCO3(71.3g) and NiCO3(47.4g) is 1 according to Li/ (Co+Ni) molar ratio
Carry out ball-milling method mixing, wherein the molar ratio of Co and Ni be 3:2, in the case that other preparation conditions are constant, preparation it is compound just
The average-size of nanocrystalline positive electrode is 55nm in the material of pole, and inside has the minimum micro- of the elementide scale of 1nm or so
Pore structure is about 1nm, main component Li rich in rock-salt defect layer thickness2RuO3、IrO2,MgO.Gained anode composite
Material is assembled into half-cell, and electrochemical property test shows: charging voltage is shown under the conditions of 0.5C multiplying power up to 4.5V
The specific capacity of 310mAh/g；Battery is still able to maintain 85% specific capacity under 6C multiplying power；The item that battery is 80% in depth of discharge
, it can be achieved that 50,000 circulations, capacity retention ratio are greater than 80% under part.
Embodiment 4
In example 2 by Li2CO3(74g)、CoCO3(71.3g) and NiCO3(47.4g) is 1 according to Li/ (Co+Ni) molar ratio
Ball-milling method mixing is carried out, wherein the molar ratio of Co and Ni is 3:2, and TiO is added2(0.01g), the constant feelings of other preparation conditions
Under condition, the average-size of nanocrystalline positive electrode is 80nm in the composite positive pole of preparation, and inside has the atom of 1nm or so
The minimum microcellular structure of cluster scale is about 2.2nm, main component TiO rich in rock-salt defect layer thickness2.Gained is multiple
Positive electrode is closed through electrochemical property test, charging voltage shows 305mAh/g's under the conditions of 0.5C multiplying power up to 4.5V
Specific capacity；The half-cell battery of assembling is still able to maintain 85% specific capacity under 6C multiplying power；Battery is 80% in depth of discharge
Under the conditions of, it can be achieved that 50,000 times circulation, capacity retention ratio be greater than 72%.
Comparative example 1
By Li2CO3With CoCO3It is 1 progress ball-milling method mixing according to Li/Co molar ratio, wet ball grinding is carried out in ethanol solution,
Ratio of grinding media to material is 25:1, and the mass ratio of solvent and mixing material is 0.5:1, and 500 revs/min of rotational speed of ball-mill, Ball-milling Time is 5 small
When.It is sintered 10 hours for 600 DEG C under argon atmosphere, normal pressure, the average-size of the positive electrode of preparation is 6 μm.By gained anode
Material assembles button cell, and electrochemical property test shows: charging voltage is shown under the conditions of 0.5C multiplying power up to 4.5V
The specific capacity (as shown in Figure 2) of 180mAh/g；Under conditions of depth of discharge is 80%, 3000 circulations can be only realized, it is cell performance
It can decay serious, or even can not work.
Comparative example 2
2 gained composite positive pole preparation process of this comparative example is same as Example 1, and difference is: being added without Li2RuO3、
IrO2, MgO material.Gained composite positive pole is assembled into half-cell, electrochemical property test shows: charging voltage is reachable
4.5V shows the specific capacity of 210mAh/g under the conditions of 0.5C multiplying power；Battery is only able to maintain 72.5% under 6C multiplying power
Specific capacity, for battery, it can be achieved that 1000 times recycle under conditions of depth of discharge is 80%, positive electrode special capacity fade is serious,
Even battery can not work normally.
Comparative example 3
3 gained composite positive pole preparation process of this comparative example is same as Example 1, and difference is: being added without in step (2)
Grapheme tube, after ball milling mixing and roasting direct processing.For gained composite positive pole through electrochemical property test, charging voltage can
Up to 4.5V, under the conditions of 0.5C multiplying power, the specific capacity of 235mAh/g is shown；Battery is only able to maintain 50% under 6C multiplying power
Specific capacity, battery is under conditions of depth of discharge is 80%, it can be achieved that 50,000 circulations, capacity retention ratio is only 55%.
Comparative example 4
4 gained composite positive pole preparation process of this comparative example is same as Example 1, and difference is: Al is added2O3(3.5g)、
RuO2(1.8g), the average-size of nanocrystalline positive electrode is 80nm in gained composite positive pole, and inside has 1nm's or so
The minimum microcellular structure of elementide scale.Wherein the thickness rich in rock-salt defect layer is about 12nm, and main component is oxygen
Change aluminium and ruthenium-oxide.Gained composite positive pole shows through electrochemical property test: charging voltage is up to 4.5V, in 0.5C multiplying power
Under the conditions of, show the specific capacity of 245mAh/g.Under 6C multiplying power, it is only able to maintain 65% specific capacity.In addition, battery is discharging
, it can be achieved that 50,000 circulations, capacity retention ratio are greater than 45% under conditions of depth is 80%.
Claims (10)
1. a kind of composite positive pole, which is characterized in that the composite positive pole includes nanocrystalline positive electrode, is coated on institute
That states nanocrystalline positive electrode surface is rich in rock salt defect layer rich in rock salt defect layer, and for carrier surface in situ cladding
The tubular graphene alkene network structure of nanocrystalline positive electrode being interconnected to form by three-dimensional grapheme tube covalent bond；
It is LiMO that the nanocrystalline positive electrode, which is chemical composition,2Layered cathode material, M be cobalt, manganese, nickel, ruthenium element at least
It is a kind of；The group rich in rock salt defect layer becomes transition metal oxide or/and lithium salts, preferably Li2RuO3、RuO2、
Al2O3、IrO2、TiO2, at least one of MgO.
2. composite positive pole according to claim 1, which is characterized in that the size of the nanocrystalline positive electrode
For 20~200 nm, and the internal minimum micropore tridimensional structure with 1 nm or less elementide scale size.
3. composite positive pole according to claim 1 or 2, which is characterized in that the thickness rich in rock salt defect layer
For 1~10 nm.
4. composite positive pole according to any one of claim 1-3, which is characterized in that in the three-dimensional grapheme tube
The number of plies of graphene is 1~10 layer, 50~300 nm of caliber, 1~20 μm of pipe range in tube wall, the content 99 of C in grapheme tube
Wt.% or more.
5. composite positive pole described in any one of -4 according to claim 1, which is characterized in that the tubular graphene alkene network
Structure accounts for the 0.1%~10% of composite positive pole gross mass.
6. a kind of preparation method of composite positive pole according to any one of claims 1-5, which is characterized in that packet
It includes:
(1) at least one of transition metal oxide, lithium salts and nanocrystalline positive electrode material precursor are chosen as raw material, then is passed through
Carry out ball milling mixing, obtain to surface and be coated with the nanocrystalline positive electrode material precursor rich in rock salt defect layer, it is described it is nanocrystalline just
Pole material precursor is Li2CO3With the carbonate of M；
(2) it is coated with the nanocrystalline positive electrode material precursor rich in rock salt defect layer and loads to three-dimensional grapheme tube structure in situ
In, then in the mixed atmosphere containing inert gas and hydrogen, calcination process is carried out at 400~1000 DEG C, is obtained described multiple
Close positive electrode.
7. preparation method according to claim 6, which is characterized in that the ball milling mixing is wet ball grinding, and parameter includes:
Ratio of grinding media to material is (10~35): 1；Solvent is at least one of water, ethyl alcohol, acetone, and the mass ratio of solvent and raw material is (0~1):
1；Rotational speed of ball-mill is 100~10000 revs/min, and Ball-milling Time is 0.5~12 hour.
8. preparation method according to claim 6 or 7, which is characterized in that the time of the roasting is 0.5~12 small
When.
9. preparation method a method according to any one of claims 6-8, which is characterized in that the pressure of the mixed atmosphere is
0.5~5 atmospheric pressure；The percent by volume of inert gas and hydrogen is (0.05~0.95) in the mixed atmosphere: 1, it is described
Inert atmosphere is at least one of argon gas and nitrogen.
10. a kind of composite positive pole according to any one of claims 1 to 5 is preparing the application in high power accumulator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910403900.3A CN110165168B (en) | 2019-05-15 | 2019-05-15 | Composite cathode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910403900.3A CN110165168B (en) | 2019-05-15 | 2019-05-15 | Composite cathode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110165168A true CN110165168A (en) | 2019-08-23 |
| CN110165168B CN110165168B (en) | 2020-08-14 |
Family
ID=67634602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910403900.3A Active CN110165168B (en) | 2019-05-15 | 2019-05-15 | Composite cathode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110165168B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110931738A (en) * | 2019-11-20 | 2020-03-27 | 广东邦普循环科技有限公司 | Complex-phase high-voltage cathode material and preparation method thereof |
| CN115121335A (en) * | 2021-03-26 | 2022-09-30 | 瑞海泊有限公司 | Positive electrode material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674326A (en) * | 2012-05-16 | 2012-09-19 | 同济大学 | Preparation method of tubular graphene with high electrochemical and capacitive property |
| CN103474629A (en) * | 2013-09-23 | 2013-12-25 | 武汉理工大学 | Semi-hollow bicontinuous line-structure coaxial nanowire material in H2V3O8/graphene tube, as well as preparation method and application of material |
| CN104347276A (en) * | 2014-09-09 | 2015-02-11 | 华中科技大学 | Graphene pipe-cladded metal oxide nanometer belt and preparation method thereof |
| CN104973588A (en) * | 2014-04-11 | 2015-10-14 | 中国科学院上海硅酸盐研究所 | High-electric-conductive, high-thermal-conductive and flexible three-dimensional graphene material and preparation method thereof |
| CN105244488A (en) * | 2015-11-16 | 2016-01-13 | 湖南杉杉能源科技股份有限公司 | Compound cladding positive pole material of lithium ion battery and preparation method of compound cladding positive pole material |
| CN105702926A (en) * | 2016-02-01 | 2016-06-22 | 浙江天能能源科技有限公司 | Ternary composite cathode material with three-dimensional network structure and preparation method of ternary composite cathode material |
| CN109244411A (en) * | 2018-09-21 | 2019-01-18 | 桑顿新能源科技有限公司 | The NCA positive electrode and its preparation method and lithium ion battery of meso-porous nano tungsten oxide cladding |
-
2019
- 2019-05-15 CN CN201910403900.3A patent/CN110165168B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674326A (en) * | 2012-05-16 | 2012-09-19 | 同济大学 | Preparation method of tubular graphene with high electrochemical and capacitive property |
| CN103474629A (en) * | 2013-09-23 | 2013-12-25 | 武汉理工大学 | Semi-hollow bicontinuous line-structure coaxial nanowire material in H2V3O8/graphene tube, as well as preparation method and application of material |
| CN104973588A (en) * | 2014-04-11 | 2015-10-14 | 中国科学院上海硅酸盐研究所 | High-electric-conductive, high-thermal-conductive and flexible three-dimensional graphene material and preparation method thereof |
| CN104347276A (en) * | 2014-09-09 | 2015-02-11 | 华中科技大学 | Graphene pipe-cladded metal oxide nanometer belt and preparation method thereof |
| CN105244488A (en) * | 2015-11-16 | 2016-01-13 | 湖南杉杉能源科技股份有限公司 | Compound cladding positive pole material of lithium ion battery and preparation method of compound cladding positive pole material |
| CN105702926A (en) * | 2016-02-01 | 2016-06-22 | 浙江天能能源科技有限公司 | Ternary composite cathode material with three-dimensional network structure and preparation method of ternary composite cathode material |
| CN109244411A (en) * | 2018-09-21 | 2019-01-18 | 桑顿新能源科技有限公司 | The NCA positive electrode and its preparation method and lithium ion battery of meso-porous nano tungsten oxide cladding |
Non-Patent Citations (2)
| Title |
|---|
| HUI BI ET AL: ""New Graphene Form of Nanoporous Monolith for Excellent Energy Storage"", 《NANO LETTERS》 * |
| HUI BI ETAL: ""A New Tubular Graphene Form of a Tetrahedrally Connected Cellular Structure"", 《ADVANCED MATERIALS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110931738A (en) * | 2019-11-20 | 2020-03-27 | 广东邦普循环科技有限公司 | Complex-phase high-voltage cathode material and preparation method thereof |
| CN110931738B (en) * | 2019-11-20 | 2021-08-03 | 广东邦普循环科技有限公司 | Complex-phase high-voltage cathode material and preparation method thereof |
| CN115121335A (en) * | 2021-03-26 | 2022-09-30 | 瑞海泊有限公司 | Positive electrode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110165168B (en) | 2020-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yan et al. | A review of spinel lithium titanate (Li4Ti5O12) as electrode material for advanced energy storage devices | |
| KR101811111B1 (en) | Bimodal lithium transition metal based oxide powder for use in a rechargeable battery | |
| CN110459736B (en) | Positive electrode material, positive electrode plate containing positive electrode material and lithium ion battery | |
| Wang et al. | Recent advances of emerging oxyhydroxide for electrochemical energy storage applications | |
| CN107437619A (en) | A kind of anode for lithium battery material and preparation method thereof | |
| CN111689528B (en) | Ternary material precursor and preparation method and application thereof | |
| CN104253267A (en) | Carbon-clad spinel lithium titanate material, production method and application thereof | |
| CN106299319B (en) | Lack the preparation method of the anode material for lithium-ion batteries of Li state material coating modification | |
| CN107768617B (en) | Lithium-sulfur battery composite cathode material and preparation method thereof | |
| CN109962233A (en) | A kind of class monocrystalline positive electrode of gradient type and preparation method thereof | |
| CN114284499B (en) | Spinel structure coated modified lithium cobaltate-based material, preparation method and lithium battery | |
| CN112510181A (en) | Composite cathode material, preparation method thereof and lithium ion battery | |
| CN104201353A (en) | Titanium-series oxide/carbon nano tube composite anode material and preparation method thereof | |
| CN111244464A (en) | Zr and Al co-doped NCM ternary cathode material and preparation method thereof | |
| CN113517424A (en) | Cobalt-free positive electrode material of high-voltage lithium ion battery and preparation method thereof | |
| CN115215389B (en) | Composite modified precursor, positive electrode material and preparation method of composite modified precursor | |
| CN103825003B (en) | A kind of three-dimensional porous Co 3o 4/ Pt/Ni combination electrode and its preparation method and application | |
| KR101772301B1 (en) | Low porosity electrodes for rechargeable batteries | |
| Ullah et al. | Recent trends in graphene based transition metal oxides as anode materials for rechargeable lithium-ion batteries | |
| CN110165168A (en) | A kind of composite positive pole and its preparation method and application | |
| CN113725424B (en) | Cobalt-free cathode material and preparation method and application thereof | |
| CN109786703B (en) | Conductive ceramic oxide coated lithium ion battery anode material and preparation method thereof | |
| CN107256963B (en) | Negative electrode material and production method, cathode and lithium ion full battery and production method | |
| US9153814B2 (en) | Mesoporous starburst carbon incorporated with metal nanocrystals or metal oxide nanocrystals, and uses thereof | |
| CN112952056A (en) | Lithium-rich manganese-based composite cathode material and preparation method and application 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221018 Address after: 214200 No. 928, Yibei Road, Qiting street, Yixing City, Wuxi City, Jiangsu Province Patentee after: Zhongke (Yixing) New Material Research Co.,Ltd. Address before: 200050 No. 1295 Dingxi Road, Shanghai, Changning District Patentee before: SHANGHAI INSTITUTE OF CERAMICS, CHINESE ACADEMY OF SCIENCES |
|
| TR01 | Transfer of patent right |