CN109192958A - Modified anode material for lithium-ion batteries in a kind of surface and preparation method thereof and lithium ion battery - Google Patents
Modified anode material for lithium-ion batteries in a kind of surface and preparation method thereof and lithium ion battery Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 76
- 239000010405 anode material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000007774 positive electrode material Substances 0.000 claims abstract description 9
- 239000011149 active material Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 23
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 229910013716 LiNi Inorganic materials 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000006245 Carbon black Super-P Substances 0.000 claims description 7
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 13
- 238000007086 side reaction Methods 0.000 abstract description 7
- 238000005520 cutting process Methods 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 239000002001 electrolyte material Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000000725 suspension Substances 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BBEAQIROQSPTKN-UHFFFAOYSA-N antipyrene Natural products C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- -1 pyrene arylamine Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Manufacturing & Machinery (AREA)
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Abstract
The present invention relates to modified anode material for lithium-ion batteries in a kind of surface and preparation method thereof and lithium ion batteries, belong to technical field of lithium ion.The modified anode material for lithium-ion batteries in the surface, chemical formula are as follows: LiNiXMn2‑xO4/ M, wherein 0 < x < 2, M are clad, the clad is hole mobile material used for solar batteries.The present invention also provides a kind of preparation methods of the modified anode material for lithium-ion batteries in surface.The present invention coats hole mobile material in active material surface, so that clad passes freely through lithium ion while completely cutting off electrolyte with positive electrode, to avoid the side reaction between electrolyte and positive electrode active materials while battery work, the decomposition for inhibiting electrolyte improves the cycle performance and stability of lithium ion battery.Preparation method provided by the invention, synthesis technology is simple and easy, and equipment requirement is low, and raw material resources are sufficient, nontoxic, harmless, pollution-free, there is good prospects for commercial application.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of anode material for lithium-ion batteries that surface is modified
And preparation method thereof and lithium ion battery.
Background technique
In recent years since environmental pollution and energy shortages are got worse, the exploitation clean and effective energy is become for facing mankind
One of main problem.Lithium ion battery is the energy storage conversion equipment being most widely used at present, with energy density
Many advantages, such as height has extended cycle life, and self discharge is few.The development in domestic lithium ion battery market is in the rapid growth of industry
Phase.The pattern that power category battery accounting rises year by year is presented in China's lithium ion battery downstream application accounting.It is with electric car etc.
The next-generation lithium ion battery technology of major application background requires it other than having traditional plurality of advantages, also to have higher
The features such as energy density, power density, long-life and low cost.
The positive electrode of lithium ion battery is mostly important one of the part of lithium ion battery, but current positive electrode
It is bad that mostly there is efficiency, and stability is poor, the series of problems such as side reaction can occur with electrolyte, and just to lithium ion battery
It is one of current most effective method of modifying that pole material, which carries out surface cladding,.But some traditional method for coating such as Al2O3、
ZrO2、MgO、V2O5Equal metal oxides and other phosphate are poor to the conductibility of lithium ion, it is suppressed that the insertion of lithium ion
And abjection, cause cycle performance to decline.
Summary of the invention
The suppression of clad existing for surface cladding process the invention solves the positive electrode of lithium ion battery in the prior art
The insertion and abjection for having made lithium ion, the technical issues of causing cycle performance of battery to decline, provide a kind of lithium that surface is modified from
Sub- cell positive material and preparation method thereof and lithium ion battery.
In order to solve the above-mentioned technical problem, technical solution of the present invention is specific as follows:
A kind of anode material for lithium-ion batteries that surface is modified, chemical formula are as follows: LiNiXMn2-xO4/ M, wherein 0 < x < 2, M
For clad, the clad is hole mobile material used for solar batteries.
In the above-mentioned technical solutions, the clad and LiNiXMn2-xO4Mass ratio be 0.0002-0.001:1.
In the above-mentioned technical solutions, the clad and LiNiXMn2-xO4Mass ratio be 0.0005-0.001:1.
In the above-mentioned technical solutions, the clad and LiNiXMn2-xO4Mass ratio be 0.0005:1.
In the above-mentioned technical solutions, the anode material for lithium-ion batteries is LiNi0.5Mn1.5O4。
In the above-mentioned technical solutions, the hole mobile material is Py-C, H111 or Spiro-OMeTAD.
A kind of preparation method for the anode material for lithium-ion batteries that surface is modified, comprising the following steps:
(1) progress high-speed stirred in solvent is added in hole mobile material and forms uniform mixed solution；
(2) positive active material LiNi is added into above-mentioned mixed solutionXMn2-xO4, it is placed on magnetic stirring apparatus and carries out surely
Fixed stirring, makes above-mentioned mixed solution sufficiently infiltrate active material in positive polar core, is evenly coated at its surface；
(3) mixed solution obtained after evenly mixing to step (2) heats, and heating temperature is 70 degrees Celsius and takes the photograph to 90
Between family name's degree, it is heated to solvent and all volatilizees, only remain solid powder；
(4) solid powder that step (3) obtains is placed into 60 degrees Celsius of vacuum drying oven and is dried, drying time
It must not be lower than 24 hours, that is, the modified anode material for lithium-ion batteries in surface is prepared.
In the above-mentioned technical solutions, the solvent is chlorobenzene.
In the above-mentioned technical solutions, the hole mobile material is Py-C, H111 or Spiro-OMeTAD.
A kind of lithium ion battery, including positive plate and negative electrode tab；
The positive plate is the anode material for lithium-ion batteries being modified by above-mentioned surface: Super-P:PVDF is with 8:1:1's
What mass ratio was mixed；
The negative electrode tab is lithium piece；
CR2032 button cell is made using PP/PE/PP diaphragm in the positive plate and negative electrode tab, as the lithium from
Sub- battery.
The beneficial effects of the present invention are:
(1) the modified anode material for lithium-ion batteries in surface provided by the invention coats hole transport in active material surface
Material, so that clad passes freely through lithium ion while completely cutting off electrolyte with positive electrode, thus in battery work
The side reaction between electrolyte and positive electrode active materials is avoided simultaneously, it is suppressed that the decomposition of electrolyte improves lithium ion battery
Cycle performance and stability.
(2) preparation method of the modified anode material for lithium-ion batteries in surface provided by the invention, synthesis technology are simple
Easy, equipment requirement is low, and raw material resources are sufficient, nontoxic, harmless, pollution-free, there is good prospects for commercial application.
Detailed description of the invention
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Fig. 1 is the head of the CR2032 button cell made of the modified anode material for lithium-ion batteries in the surface of embodiment 1
Secondary charging and discharging curve figure.
Fig. 2 is following for the CR2032 button cell made of the modified anode material for lithium-ion batteries in the surface of embodiment 1
Ring charging and discharging curve figure.
Fig. 3 is the head of the CR2032 button cell made of the modified anode material for lithium-ion batteries in the surface of embodiment 1
Secondary volt-ampere curve.
Specific embodiment
The present invention provides a kind of anode material for lithium-ion batteries that surface is modified, chemical formula are as follows: LiNiXMn2-xO4/ M,
In 0 < x < 2, M is clad, the clad be hole mobile material used for solar batteries.
It is preferred that the clad and LiNiXMn2-xO4Mass ratio be 0.0002-0.001:1.
Further preferably, the clad and LiNiXMn2-xO4Mass ratio be 0.0005-0.001:1.
Further preferably, the clad and LiNiXMn2-xO4Mass ratio be 0.0005:1.
It is preferred that the anode material for lithium-ion batteries is LiNi0.5Mn1.5O4。
It is preferred that the hole mobile material is Py-C, H111 or Spiro-OMeTAD ([bis- (4- of N, N- of 2,2', 7,7'- tetra-
Methoxyphenyl) amino] -9,9'- spiral shell, two fluorenes), most preferably Spiro-OMeTAD.
The structural formula of the Py-C is as follows:
The Py-C can refer to following document synthesis:
Jeon N J,Lee J,Noh J H,et al.Efficient inorganic-organic hybrid
perovskite sol ar cells based on pyrene arylamine derivatives as hole-
transporting materials[J].Journ al of the American Chemical Society,2013,135
(51):19087-90.
The structural formula of the H111 is as follows:
The H111 can refer to synthetic method synthesis in the prior art.
The present invention also provides a kind of preparation methods of the modified anode material for lithium-ion batteries in surface, comprising the following steps:
(1) progress high-speed stirred in solvent is added in hole mobile material and forms uniform mixed solution；It is preferred that described molten
Agent is chlorobenzene
(2) positive active material LiNi is added into above-mentioned mixed solutionXMn2-xO4, it is placed on magnetic stirring apparatus and carries out surely
Fixed stirring, makes above-mentioned mixed solution sufficiently infiltrate active material in positive polar core, is evenly coated at its surface；
(3) mixed solution obtained after evenly mixing to step (2) heats, and heating temperature is 70 degrees Celsius and takes the photograph to 90
Between family name's degree, it is heated to solvent and all volatilizees, only remain solid powder；
(4) solid powder that step (3) obtains is placed into 60 degrees Celsius of vacuum drying oven and is dried, drying time
It must not be lower than 24 hours, that is, the modified anode material for lithium-ion batteries in surface is prepared.
The present invention also provides a kind of lithium ion batteries, including positive plate and negative electrode tab；The positive plate is by above-mentioned surface
Modified anode material for lithium-ion batteries: Super-P:PVDF is mixed with the mass ratio of 8:1:1；The negative electrode tab is lithium
Piece；CR2032 button cell, the as lithium-ion electric is made using PP/PE/PP diaphragm in the positive plate and negative electrode tab
Pond.
The present invention is described in detail with reference to the accompanying drawing.
In order to have deeper understanding to the present invention, technical solution is clearly and completely retouched below with reference in embodiment
It states, but the embodiment of the present invention, just for the sake of explaining the present invention, not the limitation present invention, those skilled in the art are not having
Every other case study on implementation obtained under the premise of creative work is made, is all belonged to the scope of protection of the present invention.
Raw material used in following embodiment is commercial goods.
Embodiment 1
Hole mobile material Spiro-OMeTAD is dissolved in chlorobenzene solution with the concentration of 1mg/mL, under conditions of height turns
Full and uniform dissolution is carried out, after Spiro-OMeTAD is completely dissolved, in the mixed solution of Spiro-OMeTAD and chlorobenzene
A certain amount of LiNi is added0.5Mn1.5O4Material, the amount of addition will guarantee to make Spiro-OMeTAD and LiNi0.5Mn1.5O4Quality
Than for 0.0005:1.Obtained mixing suspension is carried out under 70 degrees Celsius with the revolving speed of 300rpm to no less than 48 hours
Stirring, allows covering material to be uniformly coated on active material LiNi0.5Mn1.5O4Surface, it is complete to the solvent in suspension
After portion's volatilization, remaining solid powder is collected, drying 24 hours in the vacuum drying oven that temperature is 60 degrees Celsius are put into, needed for obtaining
Positive electrode.By positive electrode: Super-P:PVDF is mixed and made into positive plate with the mass ratio of 8:1:1, using lithium piece as cathode
CR2032 button cell is made using PP/PE/PP diaphragm in piece.
Referring to Fig. 1-3, the electrochemical property test of battery is tested at 25 DEG C using blue electric battery test system, is surveyed
Examination voltage range is 3.5V~4.9V.Cycle performance test: charge-discharge test is carried out with the multiplying power of 1C, is recycled 500 weeks, electricity is investigated
The capacity retention ratio in pond.It is concluded that carrying out charge and discharge under 1C multiplying power, the first discharge specific capacity of battery is 119.8mAh/g
Specific discharge capacity is 109.1mAh/g after circulation 500 times, and capacity retention ratio is 91.0% or more, good cycle.
Embodiment 2
Hole mobile material Spiro-OMeTAD is dissolved in chlorobenzene solution with the concentration of 1mg/mL, under conditions of height turns
Full and uniform dissolution is carried out, after Spiro-OMeTAD is completely dissolved, in the mixed solution of Spiro-OMeTAD and chlorobenzene
A certain amount of LiNi is added0.5Mn1.5O4Material, the amount of addition will guarantee to make Spiro-OMeTAD and LiNi0.5Mn1.5O4Quality
Than for 0.0002:1.Obtained mixing suspension is carried out under 70 degrees Celsius with the revolving speed of 300rpm to no less than 48 hours
Stirring, allows covering material to be uniformly coated on active material LiNi0.5Mn1.5O4Surface, it is complete to the solvent in suspension
After portion's volatilization, remaining solid powder is collected, drying 24 hours in the vacuum drying oven that temperature is 60 degrees Celsius are put into, needed for obtaining
Positive electrode.By positive electrode: Super-P:PVDF is mixed and made into positive plate with the mass ratio of 8:1:1, using lithium piece as cathode
CR2032 button cell is made using PP/PE/PP diaphragm in piece.
Use lithium ion battery made from the modified anode material for lithium-ion batteries in surface manufactured in the present embodiment, positive material
The clad of material passes freely through lithium ion while completely cutting off electrolyte with positive electrode, to keep away while battery work
Exempt from the side reaction between electrolyte and positive electrode active materials, it is suppressed that the decomposition of electrolyte improves the circulation of lithium ion battery
Performance and stability.
Embodiment 3
Hole mobile material Spiro-OMeTAD is dissolved in chlorobenzene solution with the concentration of 1mg/mL, under conditions of height turns
Full and uniform dissolution is carried out, after Spiro-OMeTAD is completely dissolved, in the mixed solution of Spiro-OMeTAD and chlorobenzene
A certain amount of LiNi is added0.5Mn1.5O4Material, the amount of addition will guarantee to make Spiro-OMeTAD and LiNi0.5Mn1.5O4Quality
Than for 0.001:1.Obtained mixing suspension is carried out under 70 degrees Celsius with the revolving speed of 300rpm to no less than 48 hours
Stirring, allows covering material to be uniformly coated on active material LiNi0.5Mn1.5O4Surface, it is complete to the solvent in suspension
After portion's volatilization, remaining solid powder is collected, drying 24 hours in the vacuum drying oven that temperature is 60 degrees Celsius are put into, needed for obtaining
Positive electrode.By positive electrode: super-p:PVDF is mixed and made into positive plate with the mass ratio of 8:1:1, using lithium piece as cathode
CR2032 button cell is made using PP/PE/PP diaphragm in piece.
Use lithium ion battery made from the modified anode material for lithium-ion batteries in surface manufactured in the present embodiment, positive material
The clad of material passes freely through lithium ion while completely cutting off electrolyte with positive electrode, to keep away while battery work
Exempt from the side reaction between electrolyte and positive electrode active materials, it is suppressed that the decomposition of electrolyte improves the circulation of lithium ion battery
Performance and stability.
Embodiment 4
Hole mobile material Py-C is dissolved in chlorobenzene solution with the concentration of 1mg/mL, is carried out under conditions of height turns abundant
Uniform dissolution, after Py-C is completely dissolved, to a certain amount of LiNi is added in the mixed solution of Py-C and chlorobenzene0.5Mn1.5O4
Material, the amount of addition will guarantee to make Py-C and LiNi0.5Mn1.5O4Mass ratio be 0.001:1.By obtained mixing suspension with
The revolving speed of 300rpm carries out the stirring of no less than 48 hours under 90 degrees Celsius, and covering material is allow to be uniformly coated on work
Property substance LiNi0.5Mn1.5O4Surface, after in suspension solvent all volatilization after, collect remaining solid powder, be put into temperature
Degree obtained required positive electrode for drying 24 hours in 60 degrees Celsius of vacuum drying oven.By positive electrode: Super-P:PVDF
It is mixed and made into positive plate with the mass ratio of 8:1:1, using lithium piece as negative electrode tab, CR2032 button electricity is made using PP/PE/PP diaphragm
Pond.
Use lithium ion battery made from the modified anode material for lithium-ion batteries in surface manufactured in the present embodiment, positive material
The clad of material passes freely through lithium ion while completely cutting off electrolyte with positive electrode, to keep away while battery work
Exempt from the side reaction between electrolyte and positive electrode active materials, it is suppressed that the decomposition of electrolyte improves the circulation of lithium ion battery
Performance and stability.
Embodiment 5
Hole mobile material H111 is dissolved in chlorobenzene solution with the concentration of 1mg/mL, is carried out under conditions of height turns abundant
Uniform dissolution, after H111 is completely dissolved, to a certain amount of LiNi is added in the mixed solution of H111 and chlorobenzene0.5Mn1.5O4
Material, the amount of addition will guarantee to make H111 and LiNi0.5Mn1.5O4Mass ratio be 0.001:1.By obtained mixing suspension with
The revolving speed of 300rpm carries out the stirring of no less than 48 hours under 70 degrees Celsius, and covering material is allow to be uniformly coated on work
Property substance LiNi0.5Mn1.5O4Surface, after in suspension solvent all volatilization after, collect remaining solid powder, be put into temperature
Degree obtained required positive electrode for drying 24 hours in 60 degrees Celsius of vacuum drying oven.By positive electrode: Super-P:PVDF
It is mixed and made into positive plate with the mass ratio of 8:1:1, using lithium piece as negative electrode tab, CR2032 button electricity is made using PP/PE/PP diaphragm
Pond.
Use lithium ion battery made from the modified anode material for lithium-ion batteries in surface manufactured in the present embodiment, positive material
The clad of material passes freely through lithium ion while completely cutting off electrolyte with positive electrode, to keep away while battery work
Exempt from the side reaction between electrolyte and positive electrode active materials, it is suppressed that the decomposition of electrolyte improves the circulation of lithium ion battery
Performance and stability.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of modified anode material for lithium-ion batteries in surface, which is characterized in that its chemical formula are as follows: LiNiXMn2-xO4/ M,
In 0 < x < 2, M is clad, the clad be hole mobile material used for solar batteries.
2. the modified anode material for lithium-ion batteries in surface according to claim 1, which is characterized in that the clad
With LiNiXMn2-xO4Mass ratio be 0.0002-0.001:1.
3. the modified anode material for lithium-ion batteries in surface according to claim 1, which is characterized in that the clad
With LiNiXMn2-xO4Mass ratio be 0.0005-0.001:1.
4. the modified anode material for lithium-ion batteries in surface according to claim 1, which is characterized in that the clad
With LiNiXMn2-xO4Mass ratio be 0.0005:1.
5. the modified anode material for lithium-ion batteries in surface according to claim 1, which is characterized in that the lithium-ion electric
Pond positive electrode is LiNi0.5Mn1.5O4。
6. the modified anode material for lithium-ion batteries in surface described in -5 any one according to claim 1, which is characterized in that institute
Stating hole mobile material is Py-C, H111 or Spiro-OMeTAD.
7. a kind of preparation method of the modified anode material for lithium-ion batteries in surface described in claim 1-5 any one,
It is characterized in that, comprising the following steps:
(1) progress high-speed stirred in solvent is added in hole mobile material and forms uniform mixed solution；
(2) positive active material LiNi is added into above-mentioned mixed solutionXMn2-xO4, it is placed on magnetic stirring apparatus and carries out stable stir
It mixes, above-mentioned mixed solution is made sufficiently to infiltrate active material in positive polar core, be evenly coated at its surface；
(3) mixed solution obtained after evenly mixing to step (2) heats, and heating temperature is 70 degrees Celsius to 90 degrees Celsius
Between, it is heated to solvent and all volatilizees, only remain solid powder；
(4) solid powder that step (3) obtains is placed into 60 degrees Celsius of vacuum drying oven and is dried, drying time must not
Lower than 24 hours, that is, the modified anode material for lithium-ion batteries in surface is prepared.
8. the preparation method of the modified anode material for lithium-ion batteries in surface according to claim 7, which is characterized in that institute
Stating solvent is chlorobenzene.
9. the preparation method of the modified anode material for lithium-ion batteries in surface according to claim 7, which is characterized in that institute
Stating hole mobile material is Py-C, H111 or Spiro-OMeTAD.
10. a kind of lithium ion battery, including positive plate and negative electrode tab；It is characterized in that,
The positive plate is the modified anode material for lithium-ion batteries in the surface as described in claim 1-5 any one:
Super-P:PVDF is mixed with the mass ratio of 8:1:1；
The negative electrode tab is lithium piece；
CR2032 button cell, the as lithium-ion electric is made using PP/PE/PP diaphragm in the positive plate and negative electrode tab
Pond.
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| CN201811070883.8A CN109192958A (en) | 2018-09-14 | 2018-09-14 | Modified anode material for lithium-ion batteries in a kind of surface and preparation method thereof and lithium ion battery |
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|---|---|---|---|---|
| CN102723491A (en) * | 2011-12-30 | 2012-10-10 | 中国科学院广州能源研究所 | Lithium ion battery combined electrode material immersed and covered by conducting polymer and preparation method thereof |
| JP2013206579A (en) * | 2012-03-27 | 2013-10-07 | Toyota Motor Corp | Cathode and its manufacturing method and nonaqueous electrolyte secondary battery using cathode |
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| CN107507961A (en) * | 2017-07-17 | 2017-12-22 | 河南师范大学 | A kind of preparation method of conducting polymer modified anode slice of lithium ion battery |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102723491A (en) * | 2011-12-30 | 2012-10-10 | 中国科学院广州能源研究所 | Lithium ion battery combined electrode material immersed and covered by conducting polymer and preparation method thereof |
| JP2013206579A (en) * | 2012-03-27 | 2013-10-07 | Toyota Motor Corp | Cathode and its manufacturing method and nonaqueous electrolyte secondary battery using cathode |
| CN103996844A (en) * | 2014-05-26 | 2014-08-20 | 东莞市迈科科技有限公司 | Composite lithium nickel manganese oxide positive electrode material and preparation method thereof |
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