CN106299263A - 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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- 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
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- 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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- 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
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- 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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- 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 Na3[AlMo6O24H6]、K3[AlMo6O24H6]、(NH4)3[AlMo6O24H6]、(NH4)4[NiMo6O24H6]、(NH4)3[CoMo6O24H6]、K7[MnV13O38]、Na7[MnV13O38]、(NH4)7[MnV13O38]、K7[NiV13O38]、K6[Co2V10O32H2One or more in].Described covering material is conducting polymer.The invention also discloses the preparation method of above-mentioned 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, and 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 Na3[AlMo6O24H6]、K3[AlMo6O24H6]、
(NH4)3[AlMo6O24H6]、(NH4)4[NiMo6O24H6]、(NH4)3[CoMo6O24H6]、K7[MnV13O38]、
Na7[MnV13O38]、(NH4)7[MnV13O38]、K7[NiV13O38]、K6[Co2V10O32H2One in] or
Multiple.
Meanwhile, present invention also offers the preparation method of above-mentioned positive electrode active materials, comprise the steps:
S1, provide that to include that the mixed liquor of mixed solvent and inner nuclear material, described inner nuclear material are scattered in described mixed
In bonding solvent；
Described mixed solvent includes water and water soluble alcohols organic solvent；
Described inner nuclear material includes Na3[AlMo6O24H6]、K3[AlMo6O24H6]、(NH4)3[AlMo6O24H6]、
(NH4)4[NiMo6O24H6]、(NH4)3[CoMo6O24H6]、K7[MnV13O38]、Na7[MnV13O38]、
(NH4)7[MnV13O38]、K7[NiV13O38]、K6[Co2V10O32H2One 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
In the positive electrode active materials that invention provides, conducting polymer covering material is coated on inner nuclear material surface, can have
Effect improves the electrical conductivity of positive electrode active materials, makes the advantage of inner nuclear material high theory gram volume be fully used,
Thus be beneficial to be greatly improved lithium ion battery energy density.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the precursor material of the embodiment of the present invention 1 synthesis.
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 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 Na3[AlMo6O24H6]、K3[AlMo6O24H6]、(NH4)3[AlMo6O24H6]、
(NH4)4[NiMo6O24H6]、(NH4)3[CoMo6O24H6]、K7[MnV13O38]、Na7[MnV13O38]、
(NH4)7[MnV13O38]、K7[NiV13O38]、K6[Co2V10O32H2One or more in]；Described cladding
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 Na3[AlMo6O24H6] inner nuclear material can be prepared via a method which to obtain: by 7.498g
AlCl3·6H2O is dissolved in 125ml deionized water, is subsequently adding the Na of 17.5g2MoO4·6H2O,
Agitating solution, is added dropwise over hydrogen chloride solution regulation pH value of solution=1.8, then stirs at 80 DEG C and be evaporated molten
Liquid, until solution dries up, precipitate is wetting state, allows 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.
Molecular formula is K6[Co2V10O32H2] inner nuclear material can be prepared via a method which to obtain: by 7.18g
(0.052mol)KVO3It is dissolved in the deionized water that 180ml temperature is 80 DEG C, after it all dissolves, depends on
Secondary addition 4ml molar concentration is the CoSO of 1mol/l4Solution, the K of 2.16g2S2O8Pressed powder, and add
Entering salpeter solution regulation pH value is 3.5, evaporates solution at 80 DEG C subsequently, controls solution surplus in 5h
About 60ml, is filtrated to get filtrate, and adding 8ml concentration in this filtrate is the liquor kalii acetici of 1mol/l, from
So cool down and stir this solution and be precipitated thing, filter.
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, as described in aforementioned, the mean diameter of above-mentioned material is the biggest, there is the shortcoming that electrical conductivity is low, greatly
Constrain the performance of its chemical property.
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, be greatly improved the electric conductivity of positive electrode active materials, so that the theory gram of above-mentioned inner nuclear material
The feature that capacity 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, preferably past mixing
Miscellaneous conductive polymer polymer, such as, described covering material be polypyrrole, polyaniline, polyphenylene sulfide,
One in 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.
In the case of according to the invention it is preferred to, the mean diameter of described inner nuclear material is 3-100 μm.The present invention carries
In the positive electrode active materials of confession, inner nuclear material is main body, and covering material is coated on inner nuclear material surface, plays
Conductive modified effect.For above-mentioned positive electrode active materials mean diameter and inner nuclear material mean diameter difference relatively
Little, the present invention can be approximately considered the average particle of the positive electrode active materials prepared by above-mentioned inner nuclear material
Footpath is 3-100 μm.
Meanwhile, present invention also offers the preparation method of above-mentioned positive electrode active materials, comprise the steps:
S1, provide that to include that the mixed liquor of mixed solvent and inner nuclear material, described inner nuclear material are scattered in described mixed
In bonding solvent；
Described mixed solvent includes water and water soluble alcohols organic solvent；
Described inner nuclear material includes Na3[AlMo6O24H6]、K3[AlMo6O24H6]、(NH4)3[AlMo6O24H6]、
(NH4)4[NiMo6O24H6]、(NH4)3[CoMo6O24H6]、K7[MnV13O38]、Na7[MnV13O38]、
(NH4)7[MnV13O38]、K7[NiV13O38]、K6[Co2V10O32H2One 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, benzenesulfonic acid
One in sodium, petroleum sodium sulfonate, ten alkyl trimethyl ammonium bromides；Described oxidant selected from trivalent iron salt,
One in persulfate, hydrogen peroxide；Described polymerizer selected from pyrroles, aniline, diphenyl sulfide, phthalocyanine,
One in thiophene, acrylonitrile.
According to the present invention, in above-mentioned steps S1, meeting of can directly method as previously mentioned being prepared is above-mentioned
The inner nuclear material of chemical formula joins in the mixed solvent including water and water soluble alcohols organic solvent, obtains institute
State mixed liquor.
According to the present invention, in above-mentioned steps S1, under preferable case, in described mixed liquor, inner nuclear material and water
Mass ratio be 0.05-0.5:1.
In above-mentioned mixed solvent, water soluble alcohols organic solvent is 1-5:1, preferably 1-2 with the volume ratio of water:
1。
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 0.01-0.5:
0.1-3:0.1-5.
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 0.05-0.5:0.5-5.
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.Under preferable case,
The mean diameter of described positive electrode active materials is 3-100 μm.
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, under preferable case, in positive electrode, the mean diameter of positive electrode active materials is
Below 100 μm, further preferably in the case of, the mean diameter of described positive electrode active materials is 3-70 μm, more
It is preferably 3-50 μm.Now, it is beneficial to improve further the electric conductivity of positive electrode active materials, improves its discharge and recharge
Capacity, beneficially improves the energy density of the lithium ion battery prepared by this positive electrode active materials.
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 Na of 1g3[AlMo6O24H6] powder (mean diameter is 4 μm) joins 40ml second
Alcohol, with the mixed solvent that volume ratio is 3:1 of water, is stirred dispersion.Then be sequentially added into 2ml mole dense
Degree is the chlorination of 0.253mol/L for the dodecylbenzene sodium sulfonate solution of 0.0287mol/L, 2ml molar concentration
Ferrous solution, 65 μ L pyrroles (0.0629g, 0.94mmol), stir 16h and react, filter solid under room temperature
Body material, obtains positive electrode active materials.
Fig. 1 is the inner nuclear material Na added before reaction3[AlMo6O24H6] scanning electron microscope (SEM) photograph.Fig. 2 is anti-
The scanning electron microscope (SEM) photograph of the positive electrode active materials obtained after should.It can be seen that with reaction before inner nuclear material
Na3[AlMo6O24H6] compare, the positive electrode active materials outer surface obtained after reaction becomes coarse, illustrate including
Nuclear material Na3[AlMo6O24H6] surface is formed with clad.
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] powder (mean diameter is 35 μm) joins 30ml
Ethanol, with the mixed solvent that volume ratio is 2:1 of water, is stirred dispersion.Then 3ml mole it is sequentially added into
Concentration be the dodecyl sodium sulfate of 0.077mol/L, 5ml molar concentration be the Ammonium persulfate. of 0.404mol/L
Solution, 300 μ L aniline (0.307g, 3.3mmol), stir 1h and react, filter solids under room temperature
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 0.5g7[MnV13O38] powder (mean diameter is 40 μm) joins 60ml second
Alcohol, with the mixed solvent that volume ratio is 5:1 of water, is stirred dispersion.
Then being sequentially added into 3ml molar concentration is the paratoluenesulfonic acid sodium salt of 0.0383mol/L, 3ml molar concentration
For ferric chloride solution, the 100 μ L pyrroles (0.0967g, 1.44mmol) of 0.337mol/L, stir 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 4g4)7[MnV13O38] powder (mean diameter is 10 μm) joins 60ml
Ethanol, with the mixed solvent that volume ratio is 5:1 of water, is stirred dispersion.
Then being sequentially added into 2ml molar concentration is that the paratoluenesulfonic acid sodium salt of 0.01mol/L, 2ml molar concentration are
The ammonium persulfate solution of 0.1mol/L, 50 μ L aniline (0.051g, 0.55mmol), stir 16h and enter under room temperature
Row reaction, 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 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 Na processed without conducting polymer cladding in embodiment 13[AlMo6O24H6] 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)7[MnV13O38] pressed powder
Positive plate is prepared as positive electrode active materials.
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 17mAg
Carry out constant current charge-discharge circulation.
The test result obtained is shown in Table 1 and Fig. 3.Wherein, Fig. 3 is embodiment 1 and the lithium of comparative example 1 preparation
The charge-discharge performance comparison diagram of ion battery.
Table 1
| Sample | Discharge capacity (mAh/g) first |
| S1 | 400 |
| S2 | 282 |
| S3 | 260 |
| S4 | 300 |
| D1 | 376 |
| D2 | 230 |
| D3 | 200 |
| D4 | 218 |
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 (21)
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 Na3[AlMo6O24H6]、K3[AlMo6O24H6]、(NH4)3[AlMo6O24H6]、
(NH4)4[NiMo6O24H6]、(NH4)3[CoMo6O24H6]、K7[MnV13O38]、Na7[MnV13O38]、
(NH4)7[MnV13O38]、K7[NiV13O38]、K6[Co2V10O32H2One or more in]；
Described covering material is conducting polymer.
Positive electrode active materials the most according to claim 1, it is characterised in that putting down of described inner nuclear material
All particle diameters are 3-100 μm.
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, it is characterised in that described positive electrode active materials
Mean diameter be 3-100 μm.
5. according to the positive electrode active materials described in any one in claim 1-4, it is characterised in that described
In positive electrode active materials, inner nuclear material is 4-100:1 with the mass ratio of covering material.
6. the preparation method of positive electrode active materials as claimed in claim 1, it is characterised in that include as follows
Step:
S1, provide that to include that the mixed liquor of mixed solvent and inner nuclear material, described inner nuclear material are scattered in described mixed
In bonding solvent；
Described mixed solvent includes water and water soluble alcohols organic solvent；
Described inner nuclear material includes Na3[AlMo6O24H6]、K3[AlMo6O24H6]、(NH4)3[AlMo6O24H6]、
(NH4)4[NiMo6O24H6]、(NH4)3[CoMo6O24H6]、K7[MnV13O38]、Na7[MnV13O38]、
(NH4)7[MnV13O38]、K7[NiV13O38]、K6[Co2V10O32H2One 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 6, it is characterised in that described water soluble alcohols is organic molten
Agent is 1-5:1 with the volume ratio of the water in aqueous solution.
8. according to the preparation method described in claim 6 or 7, it is characterised in that described water soluble alcohols has
One or more in machine solvent selected from methanol, ethanol, propanol, butanol or isopropanol.
Preparation method the most according to claim 6, it is characterised in that the average particle of described inner nuclear material
Footpath is 3-100 μm.
Preparation method the most according to claim 6, it is characterised in that in described mixed liquor, kernel
Material is 0.05-0.5:1 with the mass ratio of water.
11. preparation methoies according to claim 6, it is characterised in that in described step S2, polymerization
The addition of agent and the weight ratio of inner nuclear material are 0.05-0.5:0.5-5.
12. preparation methoies according to claim 6, it is characterised in that in described step S2, add
Adulterant, oxidant, the mol ratio of polymerizer be 0.01-0.5:0.1-3:0.1-5.
13. preparation methoies according to claim 6, it is characterised in that in described step S2, stirring
Under the conditions of response time of carrying out control at 1-18 hour.
14. preparation methoies according to claim 6, it is characterised in that described positive electrode active materials
Mean diameter is 3-100 μm.
15. 1 kinds of positive plates, 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 1-5
Positive electrode active materials described in middle any one or by method described in any one in claim 6-14
Prepare.
16. positive plates according to claim 15, 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.
17. positive plates according to claim 16, 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%.
18. according to the positive plate described in any one in claim 15-17, it is characterised in that described positive pole
Positive electrode on collector is stratiform, and its thickness is 0.01-1mm.
19. 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 15-18 described in any one.
20. lithium ion batteries according to claim 19, it is characterised in that described negative plate is metal
Lithium sheet.
21. according to the lithium ion battery described in claim 19 or 20, it is characterised in that described barrier film selects
From polyethylene diagrams, polypropylene diaphragm or polypropylene, polyethylene/polypropylene composite film.
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