CN109309207A - A kind of positive active material and preparation method thereof, anode and lithium ion battery - Google Patents
A kind of positive active material and preparation method thereof, anode and lithium ion battery Download PDFInfo
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- CN109309207A CN109309207A CN201710629068.XA CN201710629068A CN109309207A CN 109309207 A CN109309207 A CN 109309207A CN 201710629068 A CN201710629068 A CN 201710629068A CN 109309207 A CN109309207 A CN 109309207A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to field of lithium ion battery more particularly to a kind of positive active material and preparation method thereof, anode and lithium ion batteries.The positive active material includes core, the first shell positioned at core surface and the second housing positioned at the first case surface that the material of phosphoric acid manganese iron lithium is formed；The material of first shell is carbon material, and the material of the second housing is Mo2N improves the problem of electric conductivity and the very good solution of material manganese dissolve out.
Description
Technical field
The invention belongs to field of lithium ion battery more particularly to a kind of positive active material and preparation method thereof, comprising being somebody's turn to do
The lithium ion cell positive and lithium ion battery of positive active material.
Background technique
Lithium ion battery has many advantages, such as that voltage is high, specific energy is big, has a safety feature, and is increasingly widely used,
In particular with popularizing in electric car, energy-accumulating power station etc., it is required higher and higher.
Iron manganese phosphate for lithium is the battery anode active material of a kind of high capacity, high safety, but iron manganese phosphate for lithium exists:
(1) poorly conductive；(2) under Charging state, it may occur that Fe, Mn lead to capacity attenuation from the dissolution in positive electrode active materials；(3)
Excessive digestion of metallic ion also results in the destruction of material structure, so that the problems such as cycle performance deteriorates, makes it in the industry
It is not applied slowly.In this regard, cladding is one of current main improvement means.In the prior art, such as Publication No.
In the patent of CN104218218A, lithium ferric manganese phosphate anode material for lithium-ion batteries and its preparation of a kind of core-shell structure are described
Method, the material are made of core with the outer shell for being coated on core outer surface, and the chemical component of the core is Li
(FexMnyCoz)PO4, the chemical component of the outer shell is LiCoPO4, x+y+z=1,0.5≤y≤0.7,0.05≤z≤
0.1, the outer shell of rich cobalt keeps apart soluble strong Mn with electrolyte to greatest extent, and Mn's is molten in reduction use process
Solution degree, but LiCoPO4Charge and discharge platform voltage be higher than present commercial electrolyte liquid electrochemical window, doping capacity not
It can bring into play, to influence the charge/discharge capacity of material entirety, and LiCoPO4Electric conductivity it is poor, only coat LiCoPO4
The electric conductivity of material can not be effectively improved.In the patent of Publication No. CN106058225A, a kind of core-shell structure is described
LiMn1-xFexPO4Positive electrode is made of kernel and shell, and the kernel is LiMn1-xFexPO4Nano particle；The shell
For the mixture of carbon and the metal salt containing lithium；The metal salt containing lithium is the metal phosphate containing lithium and/or the metal containing lithium
Pyrophosphate；0 < x < 0.5, the quality of the carbon are LiMn1-xFexPO4The 0.1%~10% of nanoparticle mass, but stratum nucleare
For LiMnxFe1-xPO4, shell be carbon and the metal salt containing lithium, carbon is conductive, but other Shell Materials be all it is nonconducting,
It is lower to will lead to material property.In the patent of Publication No. CN104106161A, a kind of electrode active material is described, comprising:
By a kind of core formed selected from or mixtures thereof any one of group being made up of: lithium-containing transition metal oxide, carbon materials
Material, lithium metal and metallic compound；It and include being formed on the surface of core and including lithium metal oxide particle and polymer
Shell.Lithium metal oxide particle is or mixtures thereof the particle selected from any one of the group being made up of particle: phosphoric acid
Iron lithium, lithium manganese phosphate, iron manganese phosphate for lithium, lithium titanate and lithium vanadate；Metallic compound can use in any form, such as proof gold
Category, alloy, oxide, nitride, but it still has the problem of manganese dissolves out.
Summary of the invention
There are poorly conductive, manganese to dissolve out in order to solve the problems, such as existing lithium ferric manganese phosphate material by the present invention, provides a kind of times
Rate performance is good, and positive active material for the manganese dissolution phenomenon that can be effectively reduced in use process and preparation method thereof includes this just
The anode and lithium ion battery of pole active material.
The first purpose of the invention is to provide a kind of positive active materials comprising the material of phosphoric acid manganese iron lithium is formed
Core, the first shell positioned at core surface and the second housing positioned at the first case surface；The material of first shell is carbon containing
The material of material, the second housing contains Mo2N。
A second object of the present invention is to provide a kind of preparation methods of positive active material, comprising: is attached with surface
The phosphoric acid manganese iron lithium material of carbon material is mixed with molybdenum source, then under the atmosphere of reducibility gas and nitrogen or under ammonia atmosphere
Above-mentioned positive active material is made in sintering.
Third object of the present invention is to provide a kind of lithium ion cell positive, including above-mentioned positive active material or on
State the positive active material of the preparation method preparation of positive active material.
Fourth object of the present invention is to provide a kind of lithium ion battery, including anode, cathode and be located at anode, cathode it
Between diaphragm, the just extremely above-mentioned anode.
Positive active material provided by the invention forms carbon material and Mo by the surface in situ in iron manganese phosphate for lithium2N's
Uniform shell structurre, and the iron manganese phosphate for lithium intermiscibility of the shell material and nuclear material is good, what can be formed on its surface is uniform
Clad, the positive active material of obtained core-shell structure, the carbon material of cladding can promote the electric conductivity of material, Mo2N is not only
With good electric conductivity, also there is good chemical corrosion resistance, coat Mo2N can not only promote the electric conductivity of material, also
The manganese dissolution phenomenon in use process can be effectively reduced, the especially present invention is connected outside core and second by intermediate carbon-coating
Shell Mo2N, so that nuclear material and Mo2The being completely embedded property of N is good, has preferably obstructed contact of the manganese ion with electrolyte, has improved
The cycle performance of battery.And the phosphoric acid manganese iron lithium material by the way that surface to be attached with to carbon material is mixed with molybdenum source and is being restored again
Property gas and nitrogen atmosphere under or ammonia atmosphere under be sintered positive electrode active materials be made, first being reduced property gas is for example for molybdenum source
Hydrogen reducing is at simple substance molybdenum, then nitridation reaction occurs and generates Mo2N or molybdenum source, which are directly reacted with ammonia, generates Mo2N is reacting
In the process, not only N2Or NH3Reaction is participated in, the in-situ carbon on phosphoric acid manganese iron lithium material surface also has the generation of small part surface layer carbon
Carburization reaction, to make Mo2N layers and carbon-coating contact it is closer, can also preferably completely cut off connecing for electrolyte and iron manganese phosphate for lithium
Touching reduces manganese and dissolves out phenomenon, and preparation cost is lower, is more advantageous to industrialized production.
Detailed description of the invention
Fig. 1 is the charging and discharging curve figure of the battery S10 of the embodiment of the present invention 1 and the battery DS10 of comparative example 1.
Fig. 2 is the cyclic curve figure of the battery S10 of the embodiment of the present invention 1 and the battery DS10 of comparative example 1.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
Present invention firstly provides a kind of positive active materials comprising the core of the material formation of phosphoric acid manganese iron lithium, position
The first shell in core surface and the second housing positioned at the first case surface；The material carbonaceous material of first shell, institute
The material of second housing is stated containing Mo2N improves the electric conductivity of material and solves the problems, such as manganese dissolution.
As long as the material of phosphoric acid manganese iron lithium of the invention is containing iron manganese phosphate for lithium class material such as iron manganese phosphate for lithium, mixes
The iron manganese phosphate for lithium etc. of miscellaneous modification, positive electrode active materials of the invention can have the high capacity and Gao An of iron manganese phosphate for lithium
Quan Xing, while the multiplying power of very good solution iron manganese phosphate for lithium and manganese dissolve out problem, it is preferable that the material of phosphoric acid manganese iron lithium is
LiMn1-x-yFexMyPO4/ C, 0≤x < 1,0≤y < 1, in M Co, Ni, Al, Mg, Ga and 3d transiting group metal elements at least
It is a kind of.Further preferably, the material of phosphoric acid manganese iron lithium is LiMn1-x-yFexMyPO4/ C, wherein 0.1≤x≤0.2,0≤y≤
The energy density of at least one of 0.02, M Co, Ni, Al, Mg, Ga and 3d transiting group metal elements, material is high, conductive
Property is good.
It is preferred that carbon material cracks the carbon material to be formed, the phase of the carbon-coating and nuclear material of formation in core surface in situ for carbon source
Capacitive is good, and carbon material is strong in the core surface uniform and adhesive force of cladding, is convenient for subsequent Mo2N's is prepared in situ, and is conducive to Mo2N's is tight
Close cladding.
It is preferred that on the basis of the quality of positive active material, the Mo2The total content of N and carbon material is no more than 15wt.%,
It is further ensured that the high capacity of battery.
It is preferred that on the basis of the quality of positive active material, the Mo2The content of N is 1 ~ 10wt.%, the carbon material
Content is 1 ~ 5wt.%.Further preferably, on the basis of the quality of positive active material, the Mo2The content of N is 2 ~ 5wt.%,
The content of the carbon material is 2 ~ 3wt.%.Further increase the performance of battery.
The application also proposed a kind of preparation method of positive active material, comprising: surface is attached with containing for carbon material
Iron manganese phosphate lithium material is mixed with molybdenum source, then is sintered and is made under the atmosphere of reducibility gas and nitrogen or under ammonia atmosphere
State positive active material.It is preferred that the temperature of sintering is 500 ~ 800 DEG C, the time of sintering is 2 ~ 48h, advanced optimizes clad.
It is preferred that reducibility gas is hydrogen.Reducibility gas and nitrogen can form mixed atmosphere, can also be attached with carbon using surface
The phosphoric acid manganese iron lithium material of material passes sequentially through the reducibility gas and nitrogen of high temperature after mixing with molybdenum source, the present invention is preferably also
Originality gas and nitrogen form mixed atmosphere, and the phosphoric acid manganese iron lithium material that surface is attached with carbon material is being gone back after mixing with molybdenum source
It is sintered under the mixed atmosphere of originality gas and nitrogen, it is preferable that the volume ratio of reducibility gas and nitrogen is 1/9-1.Molybdenum source elder generation quilt
Reducibility gas such as hydrogen reducing is at simple substance molybdenum, then nitridation reaction occurs and generates Mo2N or molybdenum source are directly reacted with ammonia
Generate Mo2N, during the reaction, not only N2Or NH3Reaction is participated in, the in-situ carbon on phosphoric acid manganese iron lithium material surface also has few
Carburization reaction occurs for part surface layer carbon, to make Mo2N layers and carbon-coating contact it is closer, can also preferably completely cut off electrolyte with
The contact of iron manganese phosphate for lithium reduces manganese and dissolves out phenomenon.
The phosphoric acid manganese iron lithium material that above-mentioned surface is attached with carbon material can be commercially available or be voluntarily prepared, the application couple
Preparation method does not limit particularly, for example, can using sol-gal process, solid phase method etc., solid phase method can for by lithium source,
After manganese source, source of iron, phosphorus source and carbon source ball milling high temperature sintering or spray drying after high temperature sintering；The temperature of sintering is generally 500 ~
800℃.Specific preparation process, this will not be repeated here.
Above-mentioned lithium source can be selected from LiH2PO4、Li2CO3、LiOH、CH3COOLi、LiF、LiBr、LiCl、LiI、Li2SO4、
LiNO3、Li3PO4、Li2HPO4、Li2C2O4, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium chromate, four water citric acid lithiums, tetrachloro aluminium
One or more of sour lithium and LiBF4；The manganese source is selected from MnC2O4、Mn(OH)2、MnCO3、MnSO4、Mn(NO3)2、
MnCl2Or one or more of manganese acetate；The source of iron is selected from Fe3(PO4)2、FeC2O4、FeO、FeSO4, it is ironic citrate, hard
One or more of resin acid iron and ferric acetate；Phosphorus source is selected from H3PO4、NH4H2PO4、(NH4)2HPO4、(NH4)3PO4、
Li3PO4、Li2HPO4、LiH2PO4And P2O5One or more of；The molybdenum source is selected from Mo, MoO2、MoCl5、MoO3(NH4)6Mo7O24∙4H2One or more of O；The carbon source is selected from sucrose, glucose, epoxy resin, polyvinyl alcohol and phenolic resin
One or more of equal organic carbon sources.
The application also proposed a kind of lithium ion cell positive, including above-mentioned positive active material or above-mentioned positive-active
The positive active material of the preparation method preparation of substance.
Lithium ion cell positive generally comprises the positive electrode of collector and attachment on the current collector, and positive electrode generally wraps
Positive active material and conductive agent and binder are included, positive active material herein is above-mentioned positive active material.Wherein, it glues
Any binder known in the field can be used by tying agent, such as can use polyvinylidene fluoride, polytetrafluoroethylene (PTFE) or fourth
One or more of benzene rubber.The content of binder is the 0.1-15wt.%, preferably 1- of the positive active material
7wt.%.Conductive agent can use any conductive agent known in the field, such as can use graphite, carbon fiber, carbon black, gold
Belong to one or more of powder and fiber.The content of the conductive agent is the 0.1-20wt.% of the positive active material, excellent
It is selected as 2-10wt.%.
Invention further provides a kind of lithium ion battery, including anode, cathode and between anode, cathode every
Film, the just extremely above-mentioned lithium ion cell positive.
Anode preparation method can use various methods commonly used in the art, such as with solvent by positive active material,
Binder and conductive agent are prepared into positive electrode slurries, and the additional amount of solvent is known to those skilled in the art, can basis
The requirement of the viscosity and operability of the slurry coating of anode slurries to be prepared is adjusted flexibly.It then will be obtained
Positive electrode slurries slurry is coated in dry tabletting on positive electrode collector, then cut-parts obtain anode.The temperature of the drying is usual
It is 60~140 DEG C, drying time is usually 8~20h.Solvent used in positive slurries can be in the prior art various molten
Agent, such as can be sub- selected from N-Methyl pyrrolidone (NMP), dimethylformamide (DMF), diethylformamide (DEF), dimethyl
Sulfone (DMSO), tetrahydrofuran (THF) and one or more of water and alcohols.The dosage of solvent enables the slurry to coat
Onto the conducting base.In general, the dosage of solvent makes the content 40-90 weight of positive active material in slurries
Measure %, preferably 50-85 weight %.The diaphragm of battery of the invention has electrical insulation capability and liquid retainability energy.Diaphragm can
With selected from well known to a person skilled in the art various diaphragms used in lithium ion secondary battery, such as polyolefin micro porous polyolefin membrane,
Polyethylene felt, glass mat or ultra-fine fibre glass paper.The electrolyte of battery of the invention is nonaqueous electrolytic solution.Non-aqueous solution electrolysis
Liquid is the solution that electrolyte lithium salt is formed in nonaqueous solvents, and conventional non-water power well known by persons skilled in the art can be used
Solve liquid.For example electrolyte lithium salt can be selected from lithium hexafluoro phosphate (LiPF6), lithium perchlorate (LiClO4), LiBF4
(LiBF4), hexafluoroarsenate lithium (LiAsF6), hexafluorosilicic acid lithium (LiSiF6), tetraphenylboronic acid lithium (LiB (C6H5)4), lithium chloride
(LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl4) and fluorohydrocarbon base Sulfonic Lithium (LiC (SO2CF3)3), LiCH3SO3、LiN
(SO2CF3)2One or more of.Nonaqueous solvents can be selected from chain acid esters and cyclic annular acid esters mixed solution, and wherein chain is sour
Ester can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), carbonic acid
Dipropyl (DPC) and one or more of other fluorine-containing, sulfur-bearings or the chain organosilane ester containing unsaturated bond.Cyclic annular acid esters
It can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone
And one or more of other fluorine-containing, sulfur-bearings or the cyclic annular organosilane ester containing unsaturated bond.In nonaqueous electrolytic solution, electrolysis
The concentration of matter lithium salts is generally 0.1-2 mol/L, preferably 0.8-1.2 mol/L.The present invention is to the cathode of battery without spy
Other restriction, for conventional use of cathode in the prior art, the preparation method of cathode is also known to those skilled in the art,
This is not repeated.
The preparation method of battery of the invention is well known for the person skilled in the art, in general, the system of the battery
Preparation Method includes that pole piece is placed in battery case, and electrolyte is added, then seals, obtains battery.Wherein, the method for sealing, electricity
The dosage for solving liquid is known to those skilled in the art.
Below by specific embodiment, the present invention is further described in detail.
Embodiment 1
By LiH2PO4、MnCO3、FeC2O4It is mixed with glucose according to the molar ratio of 1:0.8:0.2:0.092, is placed in stirring ball-milling
Mixed grinding 8h in machine；The presoma for being sufficiently mixed grinding preparation is placed in corundum crucible；Crucible is put into tube furnace, is led to
Enter Ar gas, begun to warm up from room temperature, the rate of heat addition is 5 DEG C/min, is warming up to 700 DEG C of roasting 10h, then naturally cools to room
LiMn is made in temperature0.8Fe0.2PO4/ C-material.By LiMn0.8Fe0.2PO4/ C and MoO3It is mixed according to mass ratio 96:5.6, is placed in and stirs
It mixes in ball mill, ethyl alcohol is added, wet-mixing grinds 6h；The presoma drying for being sufficiently mixed grinding preparation is placed on corundum earthenware
In crucible；Crucible is put into tube furnace, the H of 10% hydrogen containing volumn concentration is passed through2/N2Mixed gas adds since room temperature
Heat, the rate of heat addition are 5 DEG C/min, are warming up to 700 DEG C of roasting 15h, then cooled to room temperature, and it is 2wt.% that carbon content, which is made,
Mo2N content is the LiMn of 4wt.%0.8Fe0.2PO4/C/Mo2N composite sample S1.
Embodiment 2
By LiH2PO4、MnCO3、FeC2O4It is mixed with glucose according to the molar ratio of 1:0.9:0.1:0.046, is placed in stirring ball-milling
Mixed grinding 8h in machine；The presoma for being sufficiently mixed grinding preparation is placed in corundum crucible；Crucible is put into tube furnace, is led to
Enter Ar gas, begun to warm up from room temperature, the rate of heat addition is 5 DEG C/min, is warming up to 700 DEG C of roasting 10h, then naturally cools to room
LiMn is made in temperature0.9Fe0.1PO4/ C-material.By LiMn0.9Fe0.1PO4/ C and MoCl5It mixes, is added according to mass ratio 95:13.3
It is spray-dried after stirring 1h in water, obtained powder is placed in corundum crucible；Crucible is put into tube furnace, ammonia is passed through, from
Room temperature is begun to warm up, and the rate of heat addition is 5 DEG C/min, is warming up to 550 DEG C of roasting 20h, then cooled to room temperature, obtained carbon contain
Amount is 1wt.%, Mo2N content is the LiMn of 5wt.%0.9Fe0.1PO4/C/Mo2N composite material is labeled as S2.
Embodiment 3
By LiH2PO4、MnCO3、FeC2O4It is mixed with glucose according to the molar ratio of 1:0.8:0.2:0.13, is placed in stirring ball-milling
Mixed grinding 8h in machine；The presoma for being sufficiently mixed grinding preparation is placed in corundum crucible；Crucible is put into tube furnace, is led to
Enter Ar gas, begun to warm up from room temperature, the rate of heat addition is 5 DEG C/min, is warming up to 700 DEG C of roasting 10h, then naturally cools to room
LiMn is made in temperature0.8Fe0.2PO4/ C-material.By LiMn0.8Fe0.2PO4/ C and (NH4)6Mo7O24∙4H2O is according to mass ratio 97:5.1
Mixing is spray-dried after being added to the water stirring 1h, and obtained powder is placed in corundum crucible；Crucible is put into tube furnace, is led to
Entering ammonia, is begun to warm up from room temperature, the rate of heat addition is 5 DEG C/min, 800 DEG C of roasting 2h are warming up to, then cooled to room temperature,
It is 3wt.%, Mo that carbon content, which is made,2N content is the LiMn of 3wt.%0.8Fe0.2PO4/C/Mo2N composite material is labeled as S3.
Embodiment 4
By LiH2PO4、MnCO3、FeC2O4It is mixed with glucose according to the molar ratio of 1:0.9:0.1:0.26, is placed in stirring ball-milling
Mixed grinding 8h in machine；The presoma for being sufficiently mixed grinding preparation is placed in corundum crucible；Crucible is put into tube furnace, is led to
Enter Ar gas, begun to warm up from room temperature, the rate of heat addition is 5 DEG C/min, is warming up to 700 DEG C of roasting 10h, then naturally cools to room
LiMn is made in temperature0.9Fe0.1PO4/ C-material.By LiMn0.9Fe0.1PO4/ C and MoCl5It mixes, is added according to mass ratio 90:26.5
It is spray-dried after stirring 1h in water, obtained powder is placed in corundum crucible；Crucible is put into tube furnace, ammonia is passed through, from
Room temperature is begun to warm up, and the rate of heat addition is 5 DEG C/min, is warming up to 500 DEG C of roasting 48h, then cooled to room temperature, obtained carbon contain
Amount is 5wt.%, Mo2N content is the LiMn of 10wt.%0.9Fe0.1PO4/C/Mo2N composite material is labeled as S4.
Embodiment 5
By LiH2PO4、MnCO3、FeC2O4It is mixed with glucose according to the molar ratio of 1:0.8:0.2:0.14, is placed in stirring ball-milling
Mixed grinding 8h in machine；The presoma for being sufficiently mixed grinding preparation is placed in corundum crucible；Crucible is put into tube furnace, is led to
Enter Ar gas, begun to warm up from room temperature, the rate of heat addition is 5 DEG C/min, is warming up to 700 DEG C of roasting 10h, then naturally cools to room
LiMn is made in temperature0.8Fe0.2PO4/ C-material.By LiMn0.8Fe0.2PO4/ C and (NH4)6Mo7O24∙4H2O is according to mass ratio 95:8.6
Mixing is spray-dried after being added to the water stirring 1h, and obtained powder is placed in corundum crucible；Crucible is put into tube furnace, is led to
Enter ammonia, begun to warm up from room temperature, the rate of heat addition is 5 DEG C/min, is warming up to 700 DEG C of roasting 10h, then naturally cools to room
Temperature, it is 3wt.%, Mo that carbon content, which is made,2N content is the LiMn of 5wt.%0.8Fe0.2PO4/C/Mo2N composite material is labeled as S5.
Embodiment 6
By LiH2PO4、MnCO3、FeC2O4It is mixed with glucose according to the molar ratio of 1:0.8:0.2:0.58, is placed in stirring ball-milling
Mixed grinding 8h in machine；The presoma for being sufficiently mixed grinding preparation is placed in corundum crucible；Crucible is put into tube furnace, is led to
Enter Ar gas, begun to warm up from room temperature, the rate of heat addition is 5 DEG C/min, is warming up to 700 DEG C of roasting 10h, then naturally cools to room
LiMn is made in temperature0.8Fe0.2PO4/ C-material.By LiMn0.8Fe0.2PO4/ C and MoO3It is mixed according to mass ratio 96:21, is placed in stirring
In ball mill, ethyl alcohol is added, wet-mixing grinds 6h；The presoma drying for being sufficiently mixed grinding preparation is placed on corundum crucible
In；Crucible is put into tube furnace, 10%H is passed through2/N2Mixed gas is begun to warm up from room temperature, and the rate of heat addition is 5 DEG C/min, is risen
Temperature is to 800 DEG C of roasting 10h, and then cooled to room temperature, is made carbon content as 10wt.%, Mo2N content is 15wt.%'s
LiMn0.8Fe0.2PO4/C/Mo2N composite sample S6.
Embodiment 11 ~ 66
The production and test of battery carry out in the following way, and test cell positive plate difference positive electrode in mass ratio is (successively
Take S1-S6): acetylene black: tabletting is made the ratio of PVDF=85:10:5 after mixing, and pole piece is dried in vacuo for 24 hours in 120 DEG C
More than.It is diaphragm, 1mol/L LiPF by cathode, celgard2400 polypropylene porous film of metal lithium sheet6Ethylene carbonate
Ester (EC) and the mixed solution (volume ratio is=1:1) of dimethyl carbonate (DMC) are electrolyte.The assembling process of all batteries
It is carried out in the glove box full of argon gas, successively obtains battery sample S10-S60.
Comparative example 1
By LiH2PO4、MnC2O4、FeC2O4It is mixed with glucose according to the molar ratio of 1:0.8:0.2:0.28, is placed in stirring ball-milling
Mixed grinding 8h in machine；The presoma for being sufficiently mixed grinding preparation is placed in corundum crucible；Crucible is put into tube furnace, is led to
Enter Ar gas, begun to warm up from room temperature, the rate of heat addition is 5 DEG C/min, is warming up to 700 DEG C of roasting 10h, then naturally cools to room
The LiMn that carbon content is 6wt.% is made in temperature0.8Fe0.2PO4/ C composite is labeled as DS1.
Comparative example 2
By LiH2PO4、MnCO3And FeC2O4It is mixed according to the molar ratio of 1:0.8:0.2, is placed in mixed grinding in agitating ball mill
8h；The presoma for being sufficiently mixed grinding preparation is placed in corundum crucible；Crucible is put into tube furnace, Ar gas is passed through, from room
Temperature is begun to warm up, and the rate of heat addition is 5 DEG C/min, is warming up to 700 DEG C of roasting 10h, then cooled to room temperature, is made
LiMn0.8Fe0.2PO4Material.By LiMn0.8Fe0.2PO4And MoCl5It is mixed according to mass ratio 94:15.9, after being added to the water stirring 1h
Spray drying, obtained powder are placed in corundum crucible；Crucible is put into tube furnace, ammonia is passed through, is begun to warm up from room temperature,
The rate of heat addition is 5 DEG C/min, is warming up to 700 DEG C of roasting 10h, then cooled to room temperature, and Mo is made2N content is 6wt.%'s
LiMn0.8Fe0.2PO4/ Mo2N composite material is labeled as DS2.
Comparative example 11-22
The production and test of battery carry out in the following way, and test cell positive plate difference positive electrode in mass ratio is (successively
Take DS1-DS2): acetylene black: tabletting is made the ratio of PVDF=85:10:5 after mixing, and pole piece is dried in vacuo in 120 DEG C
More than for 24 hours.It is diaphragm, 1mol/L LiPF by cathode, celgard2400 polypropylene porous film of metal lithium sheet6Carbonic acid
The mixed solution (volume ratio is=1:1) of vinyl acetate (EC) and dimethyl carbonate (DMC) is electrolyte.The assembly of all batteries
Process carries out in the glove box full of argon gas, successively obtains battery sample DS10-DS20.
Performance test:
1, charging and discharging capacity
Charged state i.e. working electrode, which is set, by battery takes off lithium, density of charging current 0.1mA/cm2, charge to blanking voltage
4.3V, that is, out of service calculates initial charge specific capacity.
The quality that lithium specific capacity (mAh/g)=for the first time takes off lithium capacity/active material is taken off for the first time
After taking off lithium for the first time, then by battery set the embedding lithium of discharge condition i.e. working electrode, discharge current density 0.1mA/
cm2, electric discharge terminates when being discharged to blanking voltage 2.5V, calculates first discharge specific capacity.
The quality of the embedding lithium capacity/active material of embedding lithium specific capacity (mAh/g)=for the first time for the first time
Test result is as shown in figure 1 and table 1.
2, cycle performance
Constant-current charge is carried out to battery with the constant current of 0.1mA, blanking voltage is charged to, equally with the constant current of 0.1mA
To battery constant-current discharge, it is discharged to blanking voltage, is shelved 10 minutes, above step is repeated, makees continuous charge-discharge test, obtain
Battery capacity after battery 500 times circulations calculates the discharge capacitance of battery after 500 circulations.
Discharge capacity × 100% of discharge capacity/for the first time after the circulation of discharge capacitance=500 time
Test result is as shown in Figure 2 and Table 1.
Fig. 1 is that battery sample DS10 made in battery sample S10 and comparative example 1 made in embodiment 1 is filling
Charging and discharging curve when discharge-rate 0.1C.It can be found that the initial charge capacity of S10 is 155.0mAh/g, electric discharge is held for the first time
Amount is 150.7mAh/g, and the initial charge capacity of DS10 is 154.3mAh/g, and discharge capacity is 149.5mAh/g for the first time.S10 and
The capacity and voltage platform of DS10 battery do not have notable difference, illustrate Mo2The cladding of N can effectively improve as the cladding of carbon
The electric conductivity of material.
Fig. 2 is following for battery sample DS10 made in battery sample S10 and comparative example 1 made in embodiment 1
Ring life curve, it can be seen that discharge capacity is 146.3mAh/g after S10 circulating battery 500 times, and discharge capacitance is
Discharge capacity is 136.4mAh/g after 97.1%, DS10 circulating battery 500 times, and discharge capacitance 91.2% recycles result
Show LiMn0.8Fe0.2PO4/C/Mo2N composite material has than LiMn0.8Fe0.2PO4The superior charge and discharge of/C composite follow
Ring stability, illustrates Mo2The cladding of N can effectively prevent the dissolution of metal ion.
Table 1
The capacity of positive active material of the invention is high it can be seen from the test result of table 1, good cycle.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (14)
1. a kind of positive active material, which is characterized in that core that material including phosphoric acid manganese iron lithium is formed, positioned at core surface
First shell and second housing positioned at the first case surface；The material carbonaceous material of first shell, the second housing
Material contain Mo2N。
2. positive active material according to claim 1, which is characterized in that the material of the phosphoric acid manganese iron lithium is
LiMn1-x-yFexMyPO4/ C, 0≤x < 1,0≤y < 1, in M Co, Ni, Al, Mg, Ga and 3d transiting group metal elements at least
It is a kind of.
3. positive active material according to claim 1, which is characterized in that the carbon material is carbon source in core surface in situ
Crack the carbon material formed.
4. positive active material according to claim 1, which is characterized in that on the basis of the quality of positive active material,
The Mo2The total content of N and carbon material is no more than 15 wt.%.
5. positive active material according to claim 1, which is characterized in that on the basis of the quality of positive active material,
The Mo2The content of N is 1 ~ 10wt.%, and the content of the carbon material is 1 ~ 5wt.%.
6. positive active material according to claim 5, which is characterized in that on the basis of the quality of positive active material,
The Mo2The content of N is 2 ~ 5wt.%, and the content of the carbon material is 2 ~ 3wt.%.
7. a kind of preparation method of positive active material characterized by comprising surface is attached with to the phosphoric acid manganese of carbon material
Iron lithium material is mixed with molybdenum source, then is sintered under the atmosphere of reducibility gas and nitrogen or under ammonia atmosphere and claim is made
Positive active material described in 1-6 any one.
8. the preparation method of positive active material according to claim 7, which is characterized in that the surface is attached with carbon materials
The phosphoric acid manganese iron lithium material of material is prepared by lithium source, manganese source, source of iron, phosphorus source and carbon source.
9. the preparation method of positive active material according to claim 8, which is characterized in that the lithium source is selected from
LiH2PO4、Li2CO3、LiOH、CH3COOLi、LiF、LiBr、LiCl、LiI、Li2SO4、LiNO3、Li3PO4、Li2HPO4、
Li2C2O4, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium chromate, four water citric acid lithiums, in tetrachloro-lithium aluminate and LiBF4
One or more；The manganese source is selected from MnC2O4、Mn(OH)2、MnCO3、MnSO4、Mn(NO3)2、MnCl2Or one in manganese acetate
Kind is several；The source of iron is selected from Fe3(PO4)2、FeC2O4、FeO、FeSO4, ironic citrate, one in ferric stearate and ferric acetate
Kind is several；Phosphorus source is selected from H3PO4、NH4H2PO4、(NH4)2HPO4、(NH4)3PO4、Li3PO4、Li2HPO4、LiH2PO4With
P2O5One or more of；The molybdenum source is selected from Mo, MoO2、MoCl5、MoO3(NH4)6Mo7O24∙4H2One of O or several
Kind；The carbon source is selected from one or more of sucrose, glucose, epoxy resin, polyvinyl alcohol, phenolic resin.
10. the preparation method of positive active material according to claim 7, which is characterized in that the temperature of the sintering is
500 ~ 800 DEG C, the time of sintering is 2 ~ 48h.
11. the preparation method of positive active material according to claim 7, which is characterized in that the reducibility gas is
Hydrogen.
12. the preparation method of positive active material according to claim 7, which is characterized in that reducibility gas and nitrogen
Volume ratio be 1/9-1.
13. a kind of lithium ion cell positive, including positive active material described in any one of claims 1-6 or claim
The positive active material of the preparation method preparation of the described in any item positive active materials of 7-12.
14. a kind of lithium ion battery, including anode, cathode and the diaphragm between anode, cathode, described just extremely right is wanted
Anode described in asking 13.
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| CN106328889A (en) * | 2015-07-03 | 2017-01-11 | 三星Sdi株式会社 | Negative active material, lithium battery including the negative active material, and method of preparing the negative active material |
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| US11916229B2 (en) | 2022-03-31 | 2024-02-27 | Contemporary Amperex Technology Co., Limited | Positive electrode active material and preparation method therefor, positive electrode plate containing same, secondary battery, and power consuming device |
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