CN106299264A - A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery - Google Patents
A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery Download PDFInfo
- Publication number
- CN106299264A CN106299264A CN201510307216.7A CN201510307216A CN106299264A CN 106299264 A CN106299264 A CN 106299264A CN 201510307216 A CN201510307216 A CN 201510307216A CN 106299264 A CN106299264 A CN 106299264A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- electrode active
- active materials
- positive
- inner nuclear
- 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
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
-
- 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
For overcoming the problem that in prior art, lithium ion cell positive energy density is low, the invention provides a kind of positive electrode active materials, including inner nuclear material and the covering material being coated on described inner nuclear material surface；Described inner nuclear material includes (NH4)3[AlMo6O24H6]、(NH4)4[NiMo6O24H6]、(NH4)3[CoMo6O24H6]、Li3[CoMo6O24H6]、K7[MnV13O38]、Na7[MnV13O38]、(NH4)7[MnV13O38]、K7[NiV13O38One or more in]；The mean diameter of inner nuclear material is below 600nm；Covering material is conducting polymer.The invention also discloses the preparation method of this positive electrode active materials, including positive plate and the lithium ion battery of this positive electrode active materials.In the positive electrode active materials granule that the method that the present invention provides prepares, covering material is coated on inner nuclear material surface, makes the ionic conductivity of positive electrode active materials and electronic conductivity high, and effective gram volume is high, is beneficial to improve the energy density of lithium ion battery.
Description
Technical field
The present invention relates to field of lithium ion secondary, particularly relate to a kind of positive electrode active materials and preparation side thereof
Method, positive plate and lithium ion battery.
Background technology
In current daily life, lithium rechargeable battery has been widely used in mobile phone, notebook computer
And in other digital products, be indispensable energy storage device.At present, the positive pole of lithium ion battery it is applied to
Material mainly uses lithium ion to insert embedding transition metal stratiform oxide, such as LiCoO2、LiMn2O4Deng.Such
The charge and discharge process of material depends on lithium ion inserting in order and deintercalation, these materials in its lattice structure
Capacity and cyclical stability mainly determined by the stability of its crystal structure.In charge and discharge process, once
Crystal structure is destroyed or loses restorability, and the capacity of battery will decay and cycle performance deterioration.
It addition, these traditional lithium ions insert embedding positive electrode mostly can only carry out single electricity in charge and discharge process
Sub-redox reaction, causes its obtainable specific capacity to be usually less than 200mAhg-1So that lithium ion battery
Energy density relatively low.Those energy density are needed by the lithium ion battery being currently based on these tradition positive electrodes
Seek higher application, such as hybrid electric vehicle, pure electric vehicle etc., show weak point.
Summary of the invention
The technical problem to be solved is for low the asking of lithium ion battery energy density in prior art
Topic, it is provided that a kind of positive electrode active materials.
It is as follows that the present invention solves the technical scheme that above-mentioned technical problem used:
There is provided a kind of positive electrode active materials, including inner nuclear material and the cladding being coated on described inner nuclear material surface
Material；Described inner nuclear material includes (NH4)3[AlMo6O24H6]、(NH4)4[NiMo6O24H6]、
(NH4)3[CoMo6O24H6]、Li3[CoMo6O24H6]、K7[MnV13O38]、Na7[MnV13O38]、
(NH4)7[MnV13O38]、K7[NiV13O38One or more in]；The mean diameter of described inner nuclear material is
Below 600nm；Described covering material is conducting polymer.
Meanwhile, present invention also offers the preparation method of above-mentioned positive electrode active materials, comprise the steps:
S1, inner nuclear material is dissolved in the water；It is subsequently adding water soluble alcohols organic solvent, makes inner nuclear material
Recrystallization separates out, and obtains mixed liquor；
Described inner nuclear material includes (NH4)3[AlMo6O24H6]、(NH4)4[NiMo6O24H6]、
(NH4)3[CoMo6O24H6]、Li3[CoMo6O24H6]、K7[MnV13O38]、Na7[MnV13O38]、
(NH4)7[MnV13O38]、K7[NiV13O38One or more in]；
S2, adulterant, oxidant and polymerizer are added in described mixed liquor, carry out under agitation
Reaction, through filtering, obtaining described positive electrode active materials after drying；
Described adulterant is selected from dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, paratoluenesulfonic acid sodium salt, benzene
One in sodium sulfonate, petroleum sodium sulfonate, ten alkyl trimethyl ammonium bromides；Described oxidant is selected from ferric iron
One in salt, persulfate, hydrogen peroxide；Described polymerizer is selected from pyrroles, aniline, diphenyl sulfide, phthalein
One in cyanines, thiophene, acrylonitrile.
Further, present invention also offers a kind of positive plate, including plus plate current-collecting body be positioned on plus plate current-collecting body
Positive electrode, described positive electrode includes positive electrode active materials；Described positive electrode active materials be aforesaid just
Pole active material or prepared by said method.
It addition, present invention also offers the lithium ion battery using above-mentioned positive plate, including battery container and
The battery core being arranged in battery container, described battery core includes winding or the positive plate of stacking, barrier film and negative plate；
Described positive plate is foregoing positive plate.
Inventor is found by great many of experiments, and above-mentioned inner nuclear material has abnormal high theoretical gram volume.At this
Under premise, the present invention first carries out recrystallization process to this inner nuclear material so that it is particle diameter refines further, up to
To below 600nm, ionic conductivity can be effectively improved.Meanwhile, the positive electrode active materials provided in the present invention
In, conducting polymer covering material is coated on inner nuclear material surface, can be effectively improved the electricity of positive electrode active materials
Conductance, makes the advantage of inner nuclear material high theory gram volume be fully used, thus be beneficial to be greatly improved lithium from
Sub-battery energy density.
It addition, in said method, carrying out the organic solvent of interpolation during recrystallization is water soluble alcohols organic solvent,
Its required addition is considerably less, is beneficial to reduce cost, reduces and pollutes.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the inner nuclear material used in the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the positive electrode active materials of the embodiment of the present invention 1 synthesis.
Fig. 3 is the partial enlarged drawing in Fig. 2.
Fig. 4 is each element spectral distribution figure in the positive electrode active materials that the embodiment of the present invention 1 synthesizes.
Fig. 5 is the charge-discharge performance pair of the lithium ion battery of the embodiment of the present invention 1 and comparative example 1 preparation
Than figure.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, with
Lower combination accompanying drawing embodiment, is further elaborated to the present invention.Should be appreciated that described herein
Specific embodiment only in order to explain the present invention, is not intended to limit the present invention.
The positive electrode active materials that the present invention provides includes inner nuclear material and is coated on the bag on described inner nuclear material surface
Cover material；
Described inner nuclear material includes (NH4)3[AlMo6O24H6]、(NH4)4[NiMo6O24H6]、
(NH4)3[CoMo6O24H6]、Li3[CoMo6O24H6]、K7[MnV13O38]、Na7[MnV13O38]、
(NH4)7[MnV13O38]、K7[NiV13O38One or more in]；
The mean diameter of described inner nuclear material is below 600nm；
Described covering material is conducting polymer.
For above-mentioned inner nuclear material, can be prepared by conventional method.Such as:
Molecular formula is (NH4)3[AlMo6O24H6] inner nuclear material can be prepared via a method which to obtain: will
(the NH of 3.29g (2.66mmol)4)6Mo7O24·4H2O is dissolved in 70ml deionized water, after it all dissolves,
This solution of heated and boiled, is subsequently added 20ml and is dissolved with the AlCl of 0.744g (3.08mmol)3·6H2O solution.
Again boil solution 5min, subsequently temperature is transferred to 60-80 DEG C, evaporate solution.Solution surplus about 40ml
Time become cloudy, when continuing to be evaporated to remain about 20ml, a large amount of precipitation occurs, stops heating, make solution natural
Cooling.The molecular formula prepared by said method is (NH4)3[AlMo6O24H6] material particles average particle
Footpath is usually more than 19 μm.
Molecular formula is (NH4)4[NiMo6O24H6] inner nuclear material can be prepared via a method which to obtain: will
(the NH of 3.29g (2.66mmol)4)6Mo7O24·4H2O is dissolved in 70ml deionized water, after it all dissolves,
This solution of heated and boiled, is subsequently added 20ml and is dissolved with the NiSO of 0.815g (3.08mmol)4·6H2O solution.
Again boil solution 5min, subsequently temperature is transferred to 60-80 DEG C, evaporate solution.Solution surplus about 40ml
Time become cloudy, when continuing to be evaporated to remain about 20ml, a large amount of precipitation occurs, stops heating, make solution natural
Cooling.The molecular formula prepared by said method is (NH4)4[NiMo6O24H6] material particles average particle
Footpath is usually more than 20 μm.
Molecular formula is (NH4)3[CoMo6O24H6] inner nuclear material can be prepared via a method which to obtain: will
(the NH of 1.59g (1.29mmol)4)6Mo7O24·4H2O is dissolved in 70ml deionized water, after it all dissolves,
This solution of heated and boiled, is subsequently added 20ml and is dissolved with the CoSO of 0.42g (1.5mmol)4·7H2O with
0.936g(4.102mmol)(NH4)2S2O8Solution.Again boil solution 5min, subsequently temperature is transferred to
60-80 DEG C, evaporate solution.Until blue precipitate occurs, stop heating, make solution natural cooling.By upper
The molecular formula that the method for stating prepares is (NH4)3[CoMo6O24H6] material particles mean diameter usually
More than 30 μm.
Molecular formula is Li3[CoMo6O24H6] inner nuclear material can be prepared via a method which to obtain: by 1.5644g
(9mmol) Li2MoO4Being dissolved in 40ml deionized water, being subsequently added 20ml molar concentration is
The CoSO of 0.075mol/L4Solution, adds 0.936g (4.102mmol) hydrogenperoxide steam generator, then by
Being added dropwise to concentrated sulphuric acid, adjusting solution ph is 3.5.Again solution temperature is adjusted to 60-80 DEG C, evaporates solution,
Until solution occurs precipitation, stop heating, make solution natural cooling.
Molecular formula is K7[MnV13O38] inner nuclear material can be prepared via a method which to obtain: stirring and protect
Under the conditions of temperature, dissolve the KVO of 18g3In the hot water of 80 DEG C of 500ml (solution ph is about 7),
It is sequentially added into the MnSO of the sulphuric acid of the 0.5mol/l of 10ml, 0.01mol4·H2The K of O, 5.4g2S2O8Instead
Should, and evaporate simultaneously, concentrate 5.5h (now liquor capacity is about 150-200ml).Add under vigorous stirring
Hot solution, to boiling, filters, removes residue.Acetic acid-the potassium acetate of the 1mol/l of 20ml is added in filtrate
Solution, is again heated to boiling, stands, is slowly cooled to room temperature.Filter after reddish orange crystal separates out,
And wash with the acetic acid of 0.5mol/l-liquor kalii acetici, dry.By dividing that said method prepares
Minor is K7[MnV13O38] material particles mean diameter be usually more than 36 μm.
Molecular formula is (NH4)7[MnV13O38] inner nuclear material can be prepared via a method which to obtain: will
The NH of 0.01-0.1mol4VO3Being dissolved in the deionized water of 100-300ml, being subsequently adding molar concentration is
The salpeter solution of 0.1-2mol/l, molar concentration are the MnSO of 0.1-2mol/l4The solution, (NH of 1-3g4)2S2O8
Solid, evaporates solution, cooling at 60-90 DEG C subsequently, filters.By dividing that said method prepares
Minor is (NH4)7[MnV13O38] material particles mean diameter be usually more than 6 μm.
Inventor finds in an experiment, and the various materials meeting above-mentioned formula have the highest theoretical gram volume,
When being used as the positive electrode active materials of lithium ion battery, it is beneficial to improve the energy density of lithium ion battery.But
It is that the mean diameter of current existing above-mentioned material is the biggest, there is the shortcoming that electrical conductivity is low, makes greatly
The about performance of its chemical property.In the positive electrode active materials that the present invention provides, the inner nuclear material of employing
Mean diameter is below 600nm, more preferably 100-600nm.Nano level above-mentioned inner nuclear material can contract
Short lithium ion transmission range in the electrodes, thus improve ionic conductivity to a certain extent.
In the positive electrode active materials that the present invention provides, the Surface coating of above-mentioned inner nuclear material has conducting polymer bag
Cover material, the electric conductivity of positive electrode active materials can be greatly improved further, so that above-mentioned inner nuclear material
The feature that theoretical gram volume is high is given full play to, and is beneficial to improve the high rate performance of material.
According to the present invention, above-mentioned covering material can use conventional various conducting polymers, such as, described bag
Covering material is the one in polypyrrole, polyaniline, polyphenylene sulfide, poly-phthalocyanine, polythiophene, polyacrylonitrile.
In the present invention, in above-mentioned positive electrode active materials, the relative amount of covering material and inner nuclear material can be relatively
Variation on a large scale, under preferable case, in described positive electrode active materials, inner nuclear material and the matter of covering material
Amount ratio is 4-100:1.
Meanwhile, present invention also offers the preparation method of above-mentioned positive electrode active materials, comprise the steps:
S1, inner nuclear material is dissolved in the water；It is subsequently adding water soluble alcohols organic solvent, makes inner nuclear material
Recrystallization separates out, and obtains mixed liquor；
Described inner nuclear material includes (NH4)3[AlMo6O24H6]、(NH4)4[NiMo6O24H6]、
(NH4)3[CoMo6O24H6]、Li3[CoMo6O24H6]、K7[MnV13O38]、Na7[MnV13O38]、
(NH4)7[MnV13O38]、K7[NiV13O38One or more in]；
S2, adulterant, oxidant and polymerizer are added in described mixed liquor, carry out under agitation
Reaction, through filtering, obtaining described positive electrode active materials after drying；
Described adulterant is selected from dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, paratoluenesulfonic acid sodium salt, benzene
One in sodium sulfonate, petroleum sodium sulfonate, ten alkyl trimethyl ammonium bromides；Described oxidant is selected from ferric iron
One in salt, persulfate, hydrogen peroxide；Described polymerizer is selected from pyrroles, aniline, diphenyl sulfide, phthalein
One in cyanines, thiophene, acrylonitrile.
According to the present invention, in above-mentioned steps S1, the average particle of the inner nuclear material after above-mentioned recrystallization processes
Footpath is nanoscale, reaches below 600nm, and under preferable case, the mean diameter of described inner nuclear material is
100-600nm, more preferably 100-500nm, and uniform particle sizes.Nano level above-mentioned inner nuclear material is permissible
Shorten lithium ion transmission range in the electrodes, thus improve ionic conductivity to a certain extent.
According to the present invention, in above-mentioned steps S1, under preferable case, described inner nuclear material and the quality of described water
Ratio is 0.001-0.05:1.
When the inner nuclear material being dissolved in the water is carried out recrystallization, the water soluble alcohols organic solvent of interpolation and water
Volume ratio be 1-5:1, preferably 1-2:1.When using said method to carry out recrystallization, add a small amount of
Water soluble alcohols organic solvent i.e. can reach recrystallization and separates out the purpose of nano level inner nuclear material.
Water soluble alcohols organic solvent employed in above-mentioned steps can use conventional water soluble alcohols organic molten
Agent, the most specifically can be selected from one or more in methanol, ethanol, propanol, butanol or isopropanol.
After obtaining above-mentioned mixed liquor, according to the present invention, adulterant, oxidant and polymerizer need to be added to institute
State in mixed liquor, react under agitation, thus at above-mentioned inner nuclear material Surface Creation conducting polymer
Thing.
In the present invention, described adulterant selected from dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, to toluene
One in sodium sulfonate, benzene sulfonic acid sodium salt, petroleum sodium sulfonate, ten alkyl trimethyl ammonium bromides；Described oxidant
Selected from trivalent iron salt (such as ferric chloride, iron sulfate, ferric nitrate), persulfate (such as potassium peroxydisulfate,
Sodium peroxydisulfate, Ammonium persulfate .), one in hydrogen peroxide；Described polymerizer is selected from pyrroles, aniline, benzene sulfur
One in ether, phthalocyanine, thiophene, acrylonitrile.
Adulterant, oxidant, the addition of polymerizer generate conducting polymer with mutually reactive, excellent
In the case of choosing, in described step S2, the adulterant of interpolation, oxidant, the mol ratio of polymerizer are 0.001-0.1:
0.01-0.2:0.001-0.1.
It is many how many additions of above-mentioned polymerizer has influence on the conducting polymer formed on inner nuclear material surface
Few, in the present invention, for preferably improving the electric conductivity of positive electrode active materials, under preferable case, described step
In rapid S2, the addition of polymerizer and the weight ratio of inner nuclear material are 0.005-0.5:1.
In the case of according to the invention it is preferred to, in described step S2, the response time control carried out under stirring condition
System was at 1-18 hour.
In the present invention, required positive electrode active materials can be prepared by said method.
Meanwhile, present invention also offers a kind of positive plate, including plus plate current-collecting body be positioned on plus plate current-collecting body
Positive electrode, described positive electrode includes the positive electrode active materials that method as described before prepares.
Similar with existing positive plate, in the present invention, the kind of described plus plate current-collecting body has been art technology
Well known to personnel, such as, can be selected from aluminium foil, Copper Foil, Punching steel strip.
According to the present invention, in positive electrode, the content of positive electrode active materials is 20-99wt%, is preferably
30-60wt%.In the present invention, the mean diameter of positive electrode active materials is below 600nm, further preferred feelings
Under condition, the mean diameter of described positive electrode active materials is 100-600nm, more preferably 100-500nm.Now,
It is beneficial to improve further the electric conductivity of positive electrode active materials, improves its charge/discharge capacity, be beneficial to by this just improving
The energy density of the lithium ion battery that pole active material prepares.
In described positive electrode in addition to above-mentioned positive electrode active materials, the most also include positive electrode binder and selectivity
The positive conductive agent contained.
Positive electrode binder is had no particular limits by positive electrode of the present invention, can use this area
The various positive electrode binder that can be used for lithium rechargeable battery known, for example, it is possible to be Kynoar, gather
One or more in tetrafluoroethene or LA132.In described positive electrode, the content of described positive electrode binder
For 0.5-10wt%, preferably 3-10wt%, more preferably 5-10wt%.
The positive electrode that the present invention provides can also optionally contain in prior art positive electrode the most contained
Some positive conductive agent.Owing to positive conductive agent is for increasing the electric conductivity of electrode, reduce the internal resistance of battery,
Therefore the present invention preferably comprises positive conductive agent.Public affairs that described positive conductive agent kind is those skilled in the art
Knowing, such as, described positive conductive agent just can be selected from conductive carbon black, acetylene black, furnace black, CNT etc.
One or more in the conductive agent of pole.
Inventor is found surprisingly that in test, in the present invention, provides for the present invention at positive electrode active materials
On the basis of positive electrode active materials, when positive conductive agent uses conductive carbon black, can realize preferably conducting electricity effect
Really, make positive electrode active materials give play to higher gram volume, thus more obviously improve the energy of lithium ion battery
Metric density.
In described positive electrode, the content of described positive conductive agent is 0.5-70wt%, preferably 30-60wt%.
Now, on the basis of positive electrode active materials prepared by the method using the present invention to provide, lead at above-mentioned positive pole
In the case of electricity agent addition, it is beneficial to improve the gram volume of positive electrode active materials.
According to the present invention, the preparation method of above-mentioned positive plate is known, such as, and the preparation method of positive plate
It is included on plus plate current-collecting body the positive pole that coating contains containing positive electrode active materials, positive electrode binder and selectivity
The slurry of conductive agent, dry, roll-in, i.e. obtain positive plate after cut-parts.It is described dry generally at 50-160 DEG C,
Carry out at preferably 80-150 DEG C.Described roll-in and cut-parts are known to the skilled person, after roll-in completes,
Cut according to the positive pole size of prepared battery request, obtain positive plate.
Described coating step forms the positive electrode material layer that thickness is 0.01-1mm on plus plate current-collecting body.
According to the present invention, can be selected from conventional solvent for preparing the solvent of anode sizing agent, as being selected from
N-Methyl pyrrolidone (NMP), N,N-dimethylformamide (DMF), N, N-diethylformamide (DEF),
One or more of dimethyl sulfoxide (DMSO), oxolane (THF) and alcohol apoplexy due to endogenous wind.The consumption of solvent
Described slurry is enable to be coated on described collector.
Meanwhile, present invention also offers a kind of lithium ion battery using above-mentioned positive plate, including battery container
And the battery core being arranged in battery container, described battery core includes positive plate, barrier film and the negative pole set gradually
Sheet；Described positive plate is foregoing positive plate.
According to the present invention, in above-mentioned lithium ion battery, the remaining part beyond positive plate, such as battery container,
Barrier film, negative plate etc. all can use existing conventional structure and material.
Such as, like the prior art, described negative pole consist of known to one of skill in the art.Negative pole
In the negative electrode active material that comprises include to react the material forming lithium-containing compound, and lithium with lithium ion
Alloy.Under preferable case, use metal lithium sheet as negative pole.
In the present invention, as existing, barrier film is arranged between positive plate and negative plate, has electrical insulation capability
With liquid retainability energy.Described barrier film can be selected from various barrier films used in lithium rechargeable battery, preferably
In the case of, described barrier film is selected from polyethylene diagrams, polypropylene diaphragm or polypropylene, polyethylene/polypropylene composite film.
The position of described barrier film, character and kind are known to those skilled in the art.
Above-mentioned positive plate, barrier film, negative plate are set gradually, and prepares formation battery core by the way of conventional.
Above-mentioned battery core is positioned in battery container, and by positive pole ear, positive plate is welded with the positive pole of battery,
Make positive plate be connected with the positive electrical of battery, by negative lug, negative plate is welded with the negative pole of battery, make
Negative plate is connected with the negative electricity of battery.
As known to those skilled in the art, after battery core being placed in battery case, also need outside battery
Inject electrolyte in shell, make battery core be immersed in electrolyte, eventually pass plasticizing and chemical conversion i.e. can get this
The lithium rechargeable battery of bright offer.
Electrolyte is not particularly limited by the present invention, can use the various, such as, such as art technology of routine
Well known to personnel, described electrolyte is by nonaqueous solvent and is dissolved in the electrolyte of nonaqueous solvent and forms.On
State nonaqueous solvent to be not particularly limited, nonaqueous solvent up to now can be used.Described nonaqueous solvent can make
Various high boiling solvent of the prior art, low boiling point solvent or their mixture.For example, it is possible to choosing
From gamma-butyrolacton, ethylene carbonate, Ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid first third
Ester, ethyl propyl carbonic acid ester, Allyl carbonate, vinylene carbonate, diphenyl carbonate, methyl acetate, acetic acid
Ethyl ester, methyl propionate, ethyl propionate, dimethoxy-ethane, diethoxyethane, sultone and other
Fluorine-containing, sulfur-bearing or containing the ring-type organosilane ester of unsaturated bond, organic acid anhydride, N-Methyl pyrrolidone, N-first
In base Methanamide, N-methylacetamide, N,N-dimethylformamide, sulfolane, acetonitrile, dimethyl sulfoxide
At least one.
The electrolyte dissolved in described nonaqueous solvent, the present invention, also without particularly limiting, can use generally
Electrolyte for Lithium Secondary Battery Of Nonaqueous Electrolyte.Such as lithium hexafluoro phosphate (LiPF6), LiBF4
(LiBF4), hexafluoroarsenate lithium (LiSbF6), lithium perchlorate (LiClO4), fluorohydrocarbon base Sulfonic Lithium (LiCF3SO3)、
Li(CF3SO2)2N、LiC4F9SO3, high lithium aluminate (LiAlO4)、LiN(CxF2x+1SO2)(CyF2y+1SO2) (formula
Middle x and y is the natural number of 1-10), one or more in lithium chloride (LiCl) and lithium iodide (LiI).
In nonaqueous electrolytic solution, the concentration of electrolyte is generally 0.1-2.0mol/L, preferably 0.7-1.6mol/L.
By the following examples the present invention is further detailed.
Embodiment 1
The present embodiment is used for positive electrode active materials disclosed by the invention and preparation method thereof, positive plate and lithium ion are described
Battery.
1, prepared by positive electrode active materials
Under room temperature, by (the NH of 2g4)7[MnV13O38] pressed powder (mean diameter is 10 μm) is dissolved in 30ml
In distilled water, stirring and dissolving, add 90ml dehydrated alcohol under agitation, separate out precipitation, had
The mixed liquor of the inner nuclear material after recrystallization, wherein the mean diameter of inner nuclear material is 400nm.
Then be sequentially added into benzene sulfonic acid sodium salt solution that 20ml molar concentration is 0.0215mol/L, 20ml mole dense
Degree is the ferric chloride solution of 0.1387mol/L, 350 μ L pyrroles (0.339g, 5.05mmol), stirs under room temperature
Mix 16h to react, filter solid matter, obtain positive electrode active materials.
Fig. 1 is the inner nuclear material (NH added before reaction4)7[MnV13O38] scanning electron microscope (SEM) photograph.Fig. 2 is anti-
The scanning electron microscope (SEM) photograph of the positive electrode active materials obtained after should, Fig. 3 is the partial enlarged drawing in Fig. 2.Can see
Go out, with the inner nuclear material (NH before reaction4)7[MnV13O38] compare, should after the positive electrode active materials appearance that obtains
Face becomes coarse, illustrates at inner nuclear material (NH4)7[MnV13O38] surface is formed with clad.
Fig. 4 shows the spectral distribution situation of positive electrode active materials prepared by above-mentioned reaction.From Fig. 4 permissible
Finding out, main component C in benzene sulfonate-doped polypyrrole is contained in this pressed powder, and height is described
Molecule conducting film (polypyrrole) is successfully coated on (NH4)7[MnV13O38] particle surface.
2, the preparation of positive plate
By positive electrode active materials: conductive carbon black: positive electrode binder (PVDF) presses 30%:60%:10%'s
Mass percent carry out slurry prepare, be coated with, dry, roll-in, cut-parts, obtain positive plate.
3, the preparation of lithium ion battery
Using above-mentioned positive plate (diameter 7mm), metal lithium sheet is negative plate, EC:DEC=3:7 (volume
Than) (the LiPF containing 1mol/L6) it is electrolyte, make 2032 type button cell S1.
Embodiment 2
The present embodiment is used for positive electrode active materials disclosed by the invention and preparation method thereof, positive plate and lithium ion are described
Battery.
1, prepared by positive electrode active materials
Under room temperature, by (the NH of 2g4)3[CoMo6O24H6] pressed powder (mean diameter is 35 μm) is dissolved in
In 50ml distilled water, stirring and dissolving, add 100ml dehydrated alcohol under agitation, separate out precipitation,
To having the mixed liquor of the inner nuclear material after recrystallization, wherein the mean diameter of inner nuclear material is 430nm.
Then be sequentially added into 100ml molar concentration be the dodecyl sodium sulfate of 0.06mol/L, 100ml mole
Concentration is the ammonium persulfate solution of 0.277mol/L, 100 μ L aniline (0.102g, 1.1mmol), under room temperature
Stirring 1h reacts, and filters solid matter, obtains positive electrode active materials.
2, the preparation of positive plate
By positive electrode active materials: conductive carbon black: positive electrode binder (PVDF) presses the matter of 40%:55%:5%
Amount percentage ratio carry out slurry prepare, be coated with, dry, roll-in, cut-parts, obtain positive plate.
3, the preparation of lithium ion battery
Using above-mentioned positive plate (diameter 7mm), metal lithium sheet is negative plate, EC:DEC=3:7 (volume
Than) (the LiPF containing 1mol/L6) it is electrolyte, make 2032 type button cell S2.
Embodiment 3
The present embodiment is used for positive electrode active materials disclosed by the invention and preparation method thereof, positive plate and lithium ion are described
Battery.
1, prepared by positive electrode active materials
Under room temperature, by the K of 1g7[MnV13O38] powder (mean diameter is 40 μm) is dissolved in 20ml distilled water
In, stirring and dissolving, add 60ml dehydrated alcohol under agitation, separate out precipitation, obtain that there is recrystallization
After the mixed liquor of inner nuclear material, wherein the mean diameter of inner nuclear material is 450nm.
Then be sequentially added into 30ml molar concentration be the paratoluenesulfonic acid sodium salt of 0.0383mol/L, 30ml mole dense
Degree is the ferric chloride solution of 0.337mol/L, 50 μ L pyrroles (0.0484g, 0.72mmol), stirs under room temperature
4h reacts, and filters solid matter, obtains positive electrode active materials.
2, the preparation of positive plate
By positive electrode active materials: conductive carbon black: positive electrode binder (PVDF) presses the matter of 55%:42%:3%
Amount percentage ratio carry out slurry prepare, be coated with, dry, roll-in, cut-parts, obtain positive plate.
3, the preparation of lithium ion battery
Using above-mentioned positive plate (diameter 7mm), metal lithium sheet is negative plate, EC:DEC=3:7 (volume
Than) (the LiPF containing 1mol/L6) it is electrolyte, make 2032 type button cell S3.
Embodiment 4
The present embodiment is used for positive electrode active materials disclosed by the invention and preparation method thereof, positive plate and lithium ion are described
Battery.
1, prepared by positive electrode active materials
Under room temperature, by (the NH of 2g4)4[NiMo6O24H6] powder (mean diameter is 25 μm) is dissolved in 100ml
In distilled water, stirring and dissolving, add 300ml dehydrated alcohol under agitation, separate out precipitation, had
Having the mixed liquor of the inner nuclear material after recrystallization, wherein the mean diameter of inner nuclear material is 410nm.
Then be sequentially added into 20ml molar concentration be the paratoluenesulfonic acid sodium salt of 0.0383mol/L, 20ml mole dense
Degree is the ferric chloride solution of 0.337mol/L, 40 μ L pyrroles (0.0388g, 0.0578mmol), stirs under room temperature
Mix 4h to react, filter solid matter, obtain positive electrode active materials.
2, the preparation of positive plate
By positive electrode active materials: conductive carbon black: positive electrode binder (PVDF) presses 30%:60%:10%'s
Mass percent carry out slurry prepare, be coated with, dry, roll-in, cut-parts, obtain positive plate.
3, the preparation of lithium ion battery
Using above-mentioned positive plate (diameter 7mm), metal lithium sheet is negative plate, EC:DEC=3:7 (volume
Than) (the LiPF containing 1mol/L6) it is electrolyte, make 2032 type button cell S4.
Comparative example 1
This comparative example is for comparative illustration positive electrode active materials disclosed by the invention and preparation method thereof, positive plate and lithium
Ion battery.
Directly by the (NH processed without conducting polymer cladding in embodiment 14)7[MnV13O38] pressed powder
Positive plate is prepared as positive electrode active materials.
Use above-mentioned positive plate, prepare lithium ion battery D1 according to the method for embodiment 1.
Comparative example 2
This comparative example is for comparative illustration positive electrode active materials disclosed by the invention and preparation method thereof, positive plate and lithium
Ion battery.
Directly by the (NH processed without conducting polymer cladding in embodiment 24)3[CoMo6O24H6] solid
Powder prepares positive plate as positive electrode active materials.
Use above-mentioned positive plate, prepare lithium ion battery D2 according to the method for embodiment 2.
Comparative example 3
This comparative example is for comparative illustration positive electrode active materials disclosed by the invention and preparation method thereof, positive plate and lithium
Ion battery.
Directly by the K processed without conducting polymer cladding in embodiment 37[MnV13O38] pressed powder work
Positive plate is prepared for positive electrode active materials.
Use above-mentioned positive plate, prepare lithium ion battery D3 according to the method for embodiment 3.
Comparative example 4
This comparative example is for comparative illustration positive electrode active materials disclosed by the invention and preparation method thereof, positive plate and lithium
Ion battery.
Directly by the (NH processed without conducting polymer cladding in embodiment 44)4[NiMo6O24H6] solid powder
Positive plate is prepared as positive electrode active materials in end.
Use above-mentioned positive plate, prepare lithium ion battery D4 according to the method for embodiment 4.
Performance test
Above-mentioned lithium ion battery S1-S4 and D1 prepared is tested as follows:
Under 25 DEG C of environment, to battery voltage range be 1.5-4.2V, under conditions of electric current density is 17mA/g
Carry out constant current charge-discharge circulation.
The test result obtained is shown in Table 1 and Fig. 5.Wherein, Fig. 5 is embodiment 1 and comparative example 1 preparation
The charge-discharge performance comparison diagram of lithium ion battery.
Table 1
| Sample | Discharge capacity (mAh/g) first |
| S1 | 494 |
| S2 | 437 |
| S3 | 440 |
| S4 | 448 |
| D1 | 434 |
| D2 | 400 |
| D3 | 395 |
| D4 | 420 |
The test result of comparative example 1 and comparative example 1 understands, the positive-active material provided based on the present invention
The capacity of the battery that material prepares will be apparently higher than the battery prepared by the inner nuclear material of uncoated modification
Capacity.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (18)
1. a positive electrode active materials, it is characterised in that include inner nuclear material and be coated on described inner nuclear material
The covering material on surface；
Described inner nuclear material includes
(NH4)3[AlMo6O24H6]、(NH4)4[NiMo6O24H6]、(NH4)3[CoMo6O24H6]、
Li3[CoMo6O24H6]、K7[MnV13O38]、Na7[MnV13O38]、(NH4)7[MnV13O38]、K7[NiV13O38]
In one or more；
The mean diameter of described inner nuclear material is below 600nm；Described covering material is conducting polymer.
Positive electrode active materials the most according to claim 1, it is characterised in that described covering material is poly-
One in pyrroles, polyaniline, polyphenylene sulfide, poly-phthalocyanine, polythiophene, polyacrylonitrile.
Positive electrode active materials the most according to claim 1 and 2, it is characterised in that described positive-active
In material, inner nuclear material is 4-100:1 with the mass ratio of covering material.
4. the preparation method of positive electrode active materials as claimed in claim 1, it is characterised in that include as follows
Step:
S1, inner nuclear material is dissolved in the water；It is subsequently adding water soluble alcohols organic solvent, makes inner nuclear material
Recrystallization separates out, and obtains mixed liquor；
Described inner nuclear material includes (NH4)3[AlMo6O24H6]、(NH4)4[NiMo6O24H6]、
(NH4)3[CoMo6O24H6]、Li3[CoMo6O24H6]、K7[MnV13O38]、Na7[MnV13O38]、
(NH4)7[MnV13O38]、K7[NiV13O38One or more in]；
S2, adulterant, oxidant and polymerizer are added in described mixed liquor, carry out under agitation
Reaction, through filtering, obtaining described positive electrode active materials after drying；
Described adulterant is selected from dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, paratoluenesulfonic acid sodium salt, benzene
One in sodium sulfonate, petroleum sodium sulfonate, ten alkyl trimethyl ammonium bromides；Described oxidant is selected from ferric iron
One in salt, persulfate, hydrogen peroxide；Described polymerizer is selected from pyrroles, aniline, diphenyl sulfide, phthalein
One in cyanines, thiophene, acrylonitrile.
Preparation method the most according to claim 4, it is characterised in that described water soluble alcohols is organic molten
Agent is 1-5:1 with the volume ratio of water.
6. according to the preparation method described in claim 4 or 5, it is characterised in that described water soluble alcohols has
One or more in machine solvent selected from methanol, ethanol, propanol, butanol or isopropanol.
7. according to the preparation method described in claim 4 or 5, it is characterised in that putting down of described inner nuclear material
All particle diameters are 100-600nm.
8. according to the preparation method described in claim 4 or 5, it is characterised in that in described mixed liquor, interior
Nuclear material is 0.001-0.05:1 with the mass ratio of water.
9. according to the preparation method described in claim 4 or 5, it is characterised in that in described step S2,
The addition of polymerizer and the weight ratio of inner nuclear material are 0.005-0.5:1.
10. according to the preparation method described in claim 4 or 5, it is characterised in that in described step S2,
The adulterant of interpolation, oxidant, the weight ratio of polymerizer are 0.001-0.1:0.01-0.2:0.001-0.1.
11. according to the preparation method described in claim 4 or 5, it is characterised in that in described step S2,
The response time carried out under stirring condition controlled at 1-18 hour.
12. a positive plate, it is characterised in that include plus plate current-collecting body and be just positioned on plus plate current-collecting body
Pole material, described positive electrode includes positive electrode active materials；Described positive electrode active materials is claim 1-3
Positive electrode active materials described in middle any one or by method described in any one in claim 4-11
Prepare.
13. positive plates according to claim 12, it is characterised in that described positive electrode includes described
Positive electrode active materials, positive electrode binder and positive conductive agent；Described positive conductive agent is conductive carbon black.
14. positive plates according to claim 13, it is characterised in that described positive electrode binder is selected from poly-
One or more in vinylidene, politef；
In described positive electrode, the content of described positive electrode active materials is 20-99wt%, described positive electrode binder
Content be 0.5-10wt%, the content of described positive conductive agent is 0.5-70wt%.
15. according to the positive plate described in any one in claim 12-14, it is characterised in that described positive pole
Positive electrode on collector is stratiform, and its thickness is 0.01-1mm.
16. 1 kinds of lithium ion batteries, it is characterised in that include battery container and be arranged in battery container
Battery core, described battery core includes positive plate, barrier film and the negative plate set gradually；
Described positive plate is the positive plate in claim 12-15 described in any one.
17. lithium ion batteries according to claim 16, it is characterised in that described negative plate is metal
Lithium sheet.
18. according to the lithium ion battery described in claim 16 or 17, it is characterised in that described barrier film selects
From polyethylene diagrams, polypropylene diaphragm or polypropylene, polyethylene/polypropylene composite film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510307216.7A CN106299264A (en) | 2015-06-05 | 2015-06-05 | A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510307216.7A CN106299264A (en) | 2015-06-05 | 2015-06-05 | A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106299264A true CN106299264A (en) | 2017-01-04 |
Family
ID=57659943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510307216.7A Pending CN106299264A (en) | 2015-06-05 | 2015-06-05 | A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106299264A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106848188A (en) * | 2017-01-12 | 2017-06-13 | 深圳市盛邦科技有限公司 | Positive electrode active materials and preparation method thereof, positive plate and lithium ion battery |
| CN109698346A (en) * | 2018-12-29 | 2019-04-30 | 蜂巢能源科技有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery |
| CN110447127A (en) * | 2017-03-20 | 2019-11-12 | 罗伯特·博世有限公司 | Electrode active material, the method for preparing the electrode active material and the Anode and battery comprising the electrode active material |
| CN110759383A (en) * | 2019-10-31 | 2020-02-07 | 中国石油大学(华东) | Heteropolyacid crystal, preparation method thereof, secondary battery negative electrode material, secondary battery and electric device |
| CN113517418A (en) * | 2021-06-25 | 2021-10-19 | 倪尔福 | Sodium ion secondary battery and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185140A (en) * | 2011-03-31 | 2011-09-14 | 中国科学院过程工程研究所 | Preparation method of nano-network conductive polymer coated lithium iron phosphate anode material |
| JP2014060108A (en) * | 2012-09-19 | 2014-04-03 | Nagoya Institute Of Technology | Molecular cluster ion positive electrode material |
| 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 |
| CN104600314A (en) * | 2015-01-04 | 2015-05-06 | 合肥国轩高科动力能源股份公司 | Method for preparing lithium battery positive pole piece |
-
2015
- 2015-06-05 CN CN201510307216.7A patent/CN106299264A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185140A (en) * | 2011-03-31 | 2011-09-14 | 中国科学院过程工程研究所 | Preparation method of nano-network conductive polymer coated lithium iron phosphate anode material |
| JP2014060108A (en) * | 2012-09-19 | 2014-04-03 | Nagoya Institute Of Technology | Molecular cluster ion positive electrode material |
| 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 |
| CN104600314A (en) * | 2015-01-04 | 2015-05-06 | 合肥国轩高科动力能源股份公司 | Method for preparing lithium battery positive pole piece |
Non-Patent Citations (2)
| Title |
|---|
| ERFU NI等: "Anderson type polyoxomolybdate as cathode material of lithium battery and its reaction mechanism", 《JOURNAL OF POWER SOURCES》 * |
| 相彬等: "Anderson结构杂多配合物的研究进展", 《化学通报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106848188A (en) * | 2017-01-12 | 2017-06-13 | 深圳市盛邦科技有限公司 | Positive electrode active materials and preparation method thereof, positive plate and lithium ion battery |
| CN106848188B (en) * | 2017-01-12 | 2020-05-12 | 深圳市盛邦科技有限公司 | Positive electrode active material, preparation method thereof, positive plate and lithium ion battery |
| CN110447127A (en) * | 2017-03-20 | 2019-11-12 | 罗伯特·博世有限公司 | Electrode active material, the method for preparing the electrode active material and the Anode and battery comprising the electrode active material |
| CN109698346A (en) * | 2018-12-29 | 2019-04-30 | 蜂巢能源科技有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery |
| CN110759383A (en) * | 2019-10-31 | 2020-02-07 | 中国石油大学(华东) | Heteropolyacid crystal, preparation method thereof, secondary battery negative electrode material, secondary battery and electric device |
| CN110759383B (en) * | 2019-10-31 | 2022-03-22 | 中国石油大学(华东) | Heteropolyacid crystal, preparation method thereof, secondary battery negative electrode material, secondary battery and electric device |
| CN113517418A (en) * | 2021-06-25 | 2021-10-19 | 倪尔福 | Sodium ion secondary battery and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7316866B2 (en) | Ionic liquid-modified cathode and electrochemical device using the same | |
| US9005820B2 (en) | Lithium secondary battery using ionic liquid | |
| CN101699590B (en) | Hybrid supercapacitor | |
| CN111244458B (en) | Pre-lithiation electrode | |
| WO2020063371A1 (en) | Positive electrode piece and lithium-ion secondary battery | |
| KR20130076866A (en) | Method for preparing negative active material, negative electrode material and lithium ion battery | |
| CN105655642A (en) | Electrolyte and high-nickel anode lithium ion battery containing same | |
| CN104835961A (en) | Transition metal sulfide coated with carbon, preparation method and application | |
| CN106299263A (en) | A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery | |
| CN109888384B (en) | Electrolyte and battery containing the same | |
| CN106299264A (en) | A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery | |
| CN105895958A (en) | Electrolyte and lithium ion battery | |
| CN106602129A (en) | Multi-ion battery and preparation method thereof | |
| WO2020043151A1 (en) | Positive electrode plate, preparation method therefor, and lithium-ion rechargeable battery | |
| CN111834620A (en) | Lithium metal battery positive electrode, lithium metal battery and preparation method thereof | |
| CN103762350B (en) | A kind of titanium system negative material for lithium electricity and preparation method thereof | |
| CN103151563A (en) | Polymer cell and preparation method thereof | |
| CN106159207B (en) | A kind of preparation method of positive electrode active materials, positive plate and lithium ion battery | |
| JP2004071245A (en) | Nonaqueous electrolyte battery | |
| CN106299371B (en) | A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery | |
| CN105493319B (en) | Negative electrode active material, cathode and lithium rechargeable battery using the negative electrode active material | |
| CN108269992A (en) | A kind of composite anode material of high-capacity lithium ion battery and preparation method thereof | |
| CN106159253A (en) | The preparation method of a kind of positive electrode active materials, positive plate and lithium ion battery | |
| CN106469813B (en) | A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery | |
| CN106159260A (en) | The preparation method of a kind of positive electrode active materials, positive plate and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170104 |