CN103500825A - Positive electrode material of multi-element layered lithium ion battery and preparation method thereof - Google Patents
Positive electrode material of multi-element layered lithium ion battery and preparation method thereof Download PDFInfo
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- CN103500825A CN103500825A CN201310445338.3A CN201310445338A CN103500825A CN 103500825 A CN103500825 A CN 103500825A CN 201310445338 A CN201310445338 A CN 201310445338A CN 103500825 A CN103500825 A CN 103500825A
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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 discloses a positive electrode material of a multi-element layered lithium ion battery. The chemical general formula of the positive electrode material is LiNiaMbNcO2, and the Li-Ni mixed ranging degree is less than 2%; in the chemical general formula, M is a transition-metal element, N is one or more of Al, Mg, Ti and Zr, and the values of a, or b, or c meet conditions that a+b+c=1, a>0.3, and c<0.03. The preparation method is as follows: preparing a multi-element precursor by virtue of utilizing a coprecipitation method, and then performing lithiation and sintering, thereby obtaining the positive electrode material of a multi-element layered solid solution. Compared with the prior art, the positive electrode material of the multi-element layered lithium ion battery has the advantages that the Li-Ni mixed ranging degree is reduced to less than 2%, so that the positive electrode material has higher coulomb efficiency, better layer structure and stronger bond energy and shorter bond length of metal-oxygen bond and also has better cycle performance and obviously improved thermal stability at a high temperature and a high pressure.
Description
Technical field
The invention belongs to the lithium ion battery field, more particularly, the present invention relates to polynary stratiform anode material for lithium-ion batteries that a kind of applicable high voltage discharges and recharges and preparation method thereof.
Background technology
Lithium nickel cobalt manganese (NCM) ternary material (can be up to 250mAh/g because having that capacity is high, for theoretical capacity 91%), security performance is excellent and the advantage such as cheap has been subject to researcher's extensive concern, but NCM poor cycle performance under high voltage has restricted its application and development in lithium ion battery.
Because the radius of nickel ion and lithium ion is close, therefore, in the sintering process of NCM, easily cause nickel to occupy the lithium position, occur that (the Li-Ni mixing is for characterizing NCM material layer structure quality, and Ni enters in the Li layer, can hinder Li in the Li-Ni mixing
+the evolving path; And the Li ion enters in transition metal layer, can cause transition metal layer to expand, extruding Li sheath, make Li sheath spacing reduce, and both actings in conjunction, reduce the Li ionic diffusion coefficient, reduces the enclosed pasture efficiency of material; The Li-Ni mixing can obtain through Rietveld refine the Fitting Calculation by the XRD collection of illustrative plates to material, parameters R factor profile weight R in the refine the Fitting Calculation
wpwith R factor profile R
pwhile all being less than 7%, show that the refine result is accurately and reliably), make the enclosed pasture decrease in efficiency of material; Simultaneously, lithium also can occupy the nickel position, causes metal oxygen key average bond length to increase, and layer structure is unstable, and therefore, in cyclic process, the stripping of metal ion is serious, and especially the stripping of manganese is even more serious, and this causes NCM to decay and accelerate in cyclic process.Reducing the mixing of lithium nickel, suppressing the stripping of manganese and keep the NCM structural integrity is to improve the key point of NCM cycle performance under high voltage.
Introducing metallic element that bond energy is stronger can the stabilizing material structure, can reduce again the mixing of lithium nickel, be therefore modal thinking in material modification, and the most popular method under this thinking is adulterated exactly.The metallic element that the oxidation number such as doped with Al, Mg is 2 or 3 in NCM, allow in material and contain the keys such as Al-O, Mg-O that bond energy is higher, can make the structure of material more stable, Mn no longer is easy to stripping (wherein, the bond energy of Al-O is 512KJ/mol, the bond energy of Mn-O is 360KJ/mol) be adapted at using under the high charge cut-ff voltage, use the lithium ion battery of this material also correspondingly to there is better cycle performance and security performance.
Disclose in a large number the bulk phase-doped technology of NCM in prior art, related generally to presoma, doped compound and lithium salts are mixed, then by solid-phase sintering, obtained the NCM material of doping vario-property.Although these methods also can obtain adulterate body to a certain extent, but, because sintering temperature can't reach the fusing point of metal oxide, be difficult to metal oxide is embedded in the NCM matrix, therefore the NCM dopant material obtained is the composite material of metal oxide and NCM from crystal structure substantially, rather than formation solid solution, thereby can not form desirable adulterate body, can't suppress from structure the generation of Li-Ni mixing.
In view of this, necessaryly provide the mixing of a kind of lithium nickel lower polynary stratiform anode material for lithium-ion batteries, and its preparation method is provided.
Summary of the invention
The object of the invention is to: lower polynary stratiform anode material for lithium-ion batteries of a kind of lithium nickel mixing and preparation method thereof is provided.
In order to realize the foregoing invention purpose, the present inventor is through concentrated research discovery, and when the Li-Ni of polynary layered cathode material mixing is less than 2%, a small amount of Ni occupies the Li position, Ni can not take off embedding, also can serve as the support of layer structure in charging process and play the effect of rock-steady structure; When the Li-Ni mixing surpasses 2%, a large amount of Li occupy in transition metal layer, cause transition metal layer to expand, extruding lithium ion layer, and the lithium ion diffusion coefficient of material reduces, and the efficiency first that discharges and recharges of material obviously reduces (<82%, VS Li
+/ Li); The cycle performance of simultaneously paying close attention to most will become very poor, and after circulating 400 weeks, capacity is down to 50%, and from reverse XRD analysis, because Ni occupies transition metal layer in a large number, thereby subsiding appears in the layer structure of material.
Accordingly, the invention provides a kind of polynary stratiform anode material for lithium-ion batteries, by the optimization of precursor doped method, the anodal NCM material that synthetic Li-Ni mixing degree is less than 2%; The chemical general formula of described positive electrode is LiNi
am
bn
co
2, wherein, M is transition metal, and N is one or more in Al, Mg, Ti, Zr, and the value of a, b and c meets a+b+c=1, a>0.3 and c<0.03.
Compared with prior art, the polynary stratiform anode material for lithium-ion batteries of the present invention is because being contracted to Li-Ni mixing degree to be less than 2%.NCM material prepared by the present invention possesses higher enclosed pasture efficiency, better layer structure, more strong metal oxygen key bond energy and shorter metal oxygen key bond distance, therefore possesses better cycle performance under HTHP, and thermal stability has also obtained very large improvement.
As a kind of improvement of the polynary stratiform anode material for lithium-ion batteries of the present invention, the M in described chemical general formula is one or both in Co, Mn.
In order to realize the foregoing invention purpose, the present invention also provides a kind of preparation method of polynary stratiform anode material for lithium-ion batteries, and it comprises the following steps:
1) dosing: the salting liquid of nickel, cobalt, manganese is made into to the first solution, doped metal salt is made into to the second solution, complexing agent is made into to the 3rd solution, aqueous alkali is made into to the 4th solution;
2) four kinds of solution reaction: the method that adopts and flow, by step 1) are injected in reactor simultaneously, and strong stirring, be controlled at pH value between 10-14 in whipping process, and course of reaction control temperature of reaction kettle is at 40-70 ℃; After having reacted, filtration, washing, drying, obtain the hydroxide presoma of metal Uniform Doped;
3) hydroxide presoma presintering: by step 2) obtained is at 400～800 ℃ of lower presintering 2～8h, the cooling oxide precursor that obtains;
4) the oxide precursor ball milling after presintering batch mixing ball milling: by lithium source and step 3) obtained is powder;
5) mixed powder sintering: by step 4) obtained is poured in alumina crucible, then, at 300-700 ℃ of lower sintering 1-10h, continues to be warming up to 800-1200 ℃ of sintering 5-12h, obtains uniform dopant material; The two-part sintering is for Impurity removal ground is more thorough.
Compared with prior art, the preparation method of the polynary stratiform anode material for lithium-ion batteries of the present invention utilizes coprecipitation to make polynary hydroxide or carbonate precursor, obtain polynary layed solid-solution positive electrode through the lithiumation sintering again, thereby efficiently solve solid phase mixing, prepare the inhomogeneous problem of adulterate body.Because doping metals in sintering process can occupy the position of transition metal, thereby greatly reduce the generation of lithium nickel mixing; Can generate the M-O key that bond energy is higher, make lithium ion be not easy to be embedded into the transition metal position and make the structure of material more stable, therefore can be good at suppressing the stripping of Mn in NCM, make it be adapted at using under the high charge cut-ff voltage simultaneously.In addition, method of the present invention also has simple, the advantages such as controllability strong, easy realization.
A kind of improvement as the preparation method of the polynary stratiform anode material for lithium-ion batteries of the present invention, also comprise step 6) coat and process: will coat presoma and dissolve, by step 5) powder that obtains of sintering joins and coats in precursor solution, stir, filter and drying, finally, at 400-700 ℃ of sintering 2-6h, obtain the blended positive pole material that desirable metal oxide coats.To sintering, synthetic material carries out surface coating processing, can alleviate the corrosion of electrolyte to active material, make it be more suitable for using under the high charge cut-ff voltage, thereby guarantee that the lithium ion battery of this positive electrode of use possesses the security performance of better cycle performance and Geng Gao.
As a kind of improvement of the preparation method of the polynary stratiform anode material for lithium-ion batteries of the present invention, described step 1) in, manganese salt is Mn (NO
3)
2, MnCl
2, MnSO
4in at least one; Nickel salt is NiCl
2, NiSO
4, Ni (NO
3)
2in at least one; Cobalt salt is CoCl
2, CoSO
4, Co (NO
3)
2in at least one; Doped metal salt is Al salt, Mg salt, Ti salt or Zr salt.These inorganic salts are all soluble, and easy and highly basic or carbonate formation precipitation.
As a kind of improvement of the preparation method of the polynary stratiform anode material for lithium-ion batteries of the present invention, described step 1) in highly basic be NaOH or KOH.The solubility of these several materials is higher, and is easy to form precipitation with inorganic salts.
As a kind of improvement of the preparation method of the polynary stratiform anode material for lithium-ion batteries of the present invention, described step 1) in complexing agent be ammoniacal liquor or aminocarboxylate, as protein, amino acid, sodium ethylene diamine tetracetate (EDTA) etc.
As a kind of improvement of the preparation method of the polynary stratiform anode material for lithium-ion batteries of the present invention, described step 2) reactor in inert gas or the nitrogen protections such as argon gas are arranged.This is because the metal appraised at the current rate affects follow-up preparation manipulation than being easier to be oxidized to high valence state, therefore utilizes inert gas or nitrogen to prevent that presoma is oxidized.
As a kind of improvement of the preparation method of the polynary stratiform anode material for lithium-ion batteries of the present invention, described step 3) in duration of ball milling be 3-12h.This is because of the too short abundant mixing that is unfavorable for raw material of ball milling duration, the oversize waste that can cause again resource of ball milling duration.
As a kind of improvement of the preparation method of the polynary stratiform anode material for lithium-ion batteries of the present invention, described step 3) after sintering, also need to be pulverized and sieve processing, in order to control the granularity of gained positive electrode.
As a kind of improvement of the preparation method of the polynary stratiform anode material for lithium-ion batteries of the present invention, described step 4) the lithium source be LiOH, Li
2o or Li
2cO
3.
As a kind of improvement of the preparation method of the polynary stratiform anode material for lithium-ion batteries of the present invention, described step 6) the coating presoma be one or more in Al source, Mg source, Ti source or Zr source.
Embodiment
In order to make goal of the invention of the present invention, technical scheme and useful technique effect more clear, below in conjunction with embodiment, the present invention is further elaborated.Should be understood that, the embodiment described in this specification is only in order to explain the present invention, and not in order to limit the present invention, the formula of embodiment, ratio etc. can be suited measures to local conditions to make a choice and result be there is no to substantial effect.
In the present invention, the computational methods of Li-Ni mixing degree are:
1: the NCM powder is carried out to XRD and ICP test, obtain XRD initial data and Li, Ni, Co and Mn content;
2: import XRD data file (10 column data) and instrument parameter, according to the sequencing of back end, zero point, peak shape, cell parameter, atomic coordinates, vibration factor, occupation rate and Li-Ni mixing, carry out refine, finally obtain Li-Ni mixing data; In the refine the Fitting Calculation, parameters R factor profile weight R
wpwith R factor profile R
pwhile all being less than 7%, show the refine result accurately and reliably, otherwise refine again.
The invention provides polynary stratiform anode material for lithium-ion batteries and preparation method thereof, is below specific embodiment.
Embodiment 1
The chemical formula of the present embodiment anode material for lithium-ion batteries is LiNi
0.5co
0.2mn
0.29al
0.01o
2, its preparation method comprises the following steps:
1) dosing: by Mn (NO
3)
2, Ni (NO
3)
2and Co (NO
3)
23:5:2.9 is made into the first solution in molar ratio, by Al (NO
3)
3be made into the second solution, EDTA is made into to the 3rd solution, NaOH is made into to the 4th solution;
2) reaction: the method that adopts and flow, four kinds of solution are injected in reactor simultaneously, strong stirring, control pH value between 10-14 in whipping process, and course of reaction is controlled temperature of reaction kettle at 40-70 ℃; After having reacted, filtration, washing, drying, obtain the hydroxide presoma of Al Uniform Doped, and inert gas or nitrogen protection are arranged in reactor;
3) presoma presintering: by step 2) is at 500 ℃ of lower presintering 5h, the cooling oxide precursor that obtains;
4) it is powder that the presoma after presintering batch mixing ball milling: by lithium source and step 3) obtained joins ball milling in ball grinder;
5) mixed powder sintering: by step 4) obtained is poured in alumina crucible, then, at 300-700 ℃ of lower sintering 5h, continues to be warming up to 800-1200 ℃ of sintering 10h, obtains the positive electrode LiNi of Uniform Doped
0.5co
0.2mn
0.29al
0.01o
2.
As calculated, the positive electrode LiNi that embodiment 1 makes
0.5co
0.2mn
0.29al
0.01o
2lithium nickel mixing degree be 1.25%.
Embodiment 2
The chemical formula of the present embodiment anode material for lithium-ion batteries is LiNi
0.4co
0.2mn
0.39mg
0.01o
2, its preparation method comprises the following steps:
1) dosing: by Mn (NO
3)
2, Ni (NO
3)
2and Co (NO
3)
23.9:4:2 is made into the first solution in molar ratio, by Mg (NO
3)
2be made into the second solution, EDTA is made into to the 3rd solution, NaOH is made into to the 4th solution;
2) reaction: the method that adopts and flow, four kinds of solution are injected in reactor simultaneously, strong stirring, control pH value between 10-14 in whipping process, and course of reaction is controlled temperature of reaction kettle at 40-70 ℃; After having reacted, filtration, washing, drying, obtain the hydroxide presoma of Mg Uniform Doped, and inert gas or nitrogen protection are arranged in reactor;
3) presoma presintering: by step 2) is at 500 ℃ of presintering 5h, the cooling oxide precursor that obtains;
4) it is powder that the presoma after presintering batch mixing ball milling: by lithium source and step 3) obtained joins ball milling in ball grinder;
5) mixed powder sintering: by step 4) obtained is poured in alumina crucible, then, at 300-700 ℃ of lower sintering 7h, continues to be warming up to 800-1200 ℃ of sintering 8h, obtains the positive electrode LiNi of Uniform Doped
0.4co
0.2mn
0.39mg
0.01o
2.
As calculated, the positive electrode LiNi that embodiment 2 makes
0.4co
0.2mn
0.39mg
0.01o
2lithium nickel mixing degree be 1.31%.
Embodiment 3
The present embodiment anode material for lithium-ion batteries chemical formula is LiNi
0.5co
0.2mn
0.285al
0.01mg
0.005o
2, its preparation method comprises the following steps:
1) dosing: by Mn (NO
3)
2, Ni (NO
3)
2and Co (NO
3)
22.85:5:2 is made into the first solution in molar ratio, by Mg (NO
3)
2be made into the second solution, EDTA is made into to the 3rd solution, NaOH is made into to the 4th solution;
2) reaction: the method that adopts and flow, by four kinds of solution, be injected in reactor simultaneously, strong stirring, control pH value in whipping process between 10-14, course of reaction is controlled temperature of reaction kettle at 40-70 ℃, after having reacted, and filtration, washing, drying, obtain the hydroxide presoma of Mg Uniform Doped, inert gas or nitrogen protection are arranged in reactor;
3) presoma presintering: by step 2) is at 500 ℃ of presintering 5h, the cooling oxide precursor that obtains;
4) it is powder that the presoma after presintering batch mixing ball milling: by lithium source and step 3) obtained joins ball milling in ball grinder;
5) mixed powder sintering: by step 4) obtained is poured in alumina crucible, then, at 300-700 ℃ of lower sintering 1-10h, continues to be warming up to 800-1200 ℃ of sintering 5-12h, obtains uniform dopant material;
6) powder that coating processing: at first the aluminium source is dissolved, then by step 5) sintering obtains joins in aluminum solutions, stirs, filters and drying, finally at 400-700 ℃ of sintering 2-6h, obtains the blended positive pole material LiNi of desirable Al coating
0.5co
0.2mn
0.285al
0.01mg
0.005o
2.
As calculated, the positive electrode LiNi that embodiment 3 makes
0.5co
0.2mn
0.285al
0.01mg
0.005o
2lithium nickel mixing degree be 1.46%.
Embodiment 4
The chemical formula of the anode material for lithium-ion batteries provided in the present embodiment can be expressed as LiNi
0.5co
0.2mn
0.28al
0.01mg
0.005ti
0.005o
2, its preparation method comprises the following steps:
1) dosing: by Mn (NO
3)
2, Ni (NO
3)
2and Co (NO
3)
22.8:5:2 is made into the first solution in molar ratio, by Al (NO
3)
3and Mg (NO
3)
2be made into the second solution, EDTA is made into to the 3rd solution, NaOH is made into to the 4th solution;
2) reaction: the method that adopts and flow, by four kinds of solution, be injected in reactor simultaneously, strong stirring, control pH value in whipping process between 10-14, course of reaction is controlled temperature of reaction kettle at 40-70 ℃, after having reacted, and filtration, washing, drying, obtain the hydroxide presoma of Al and Mg Uniform Doped, inert gas or nitrogen protection are arranged in reactor;
3) presoma presintering: by step 2) is at 500 ℃ of presintering 5h, the cooling oxide precursor that obtains;
4) it is powder that the presoma after presintering batch mixing ball milling: by lithium source and step 3) obtained joins ball milling in ball grinder;
5) mixed powder sintering: by step 4) obtained is poured in alumina crucible, then, at 300-700 ℃ of lower sintering 1-10h, continues to be warming up to 800-1200 ℃ of sintering 5-12h, obtains uniform dopant material;
6) powder that coating processing: at first the titanium source is dissolved, then by step 5) sintering obtains joins in titanium solution, stirs, filters and drying, finally at 400-700 ℃ of sintering 2-6h, obtains the blended positive pole material LiNi of desirable titanium coating
0.5co
0.2mn
0.28al
0.01mg
0.005ti
0.005o
2.
As calculated, the positive electrode LiNi that embodiment 4 makes
0.5co
0.2mn
0.28al
0.01mg
0.005ti
0.005o
2lithium nickel mixing degree be 1.15%.
Embodiment 5
The chemical formula of the present embodiment anode material for lithium-ion batteries is LiNi
0.8co
0.1mn
0.08al
0.01ti
0.01o
2, its preparation method comprises the following steps:
1) dosing: by Mn (NO
3)
2, Ni (NO
3)
2and Co (NO
3)
20.8:8:1 is made into the first solution in molar ratio, by Al (NO
3)
3be made into the second solution, EDTA is made into to the 3rd solution, NaOH is made into to the 4th solution;
2) reaction: the method that adopts and flow, by four kinds of solution, be injected in reactor simultaneously, strong stirring, control pH value in whipping process between 10-14, course of reaction is controlled temperature of reaction kettle at 40-70 ℃, after having reacted, and filtration, washing, drying, obtain the hydroxide presoma of Al Uniform Doped, inert gas or nitrogen protection are arranged in reactor;
3) presoma presintering: by step 2) is at 500 ℃ of presintering 5h, the cooling oxide precursor that obtains;
4) it is powder that the presoma after presintering batch mixing ball milling: by lithium source and step 3) obtained joins ball milling in ball grinder;
5) mixed powder sintering: by step 4) obtained is poured in alumina crucible, then, at 300-700 ℃ of lower sintering 1-10h, continues to be warming up to 800-1200 ℃ of sintering 5-12h, obtains uniform dopant material;
6) powder that coating processing: at first the titanium source is dissolved, then by step 5) sintering obtains joins in titanium solution, stirs, filters and drying, finally at 400-700 ℃ of sintering 2-6h, obtains the blended positive pole material LiNi of desirable titanium coating
0.8co
0.1mn
0.08al
0.01ti
0.01o
2.
As calculated, the positive electrode LiNi that embodiment 5 makes
0.8co
0.1mn
0.08al
0.01ti
0.01o
2lithium nickel mixing degree be 1.97%.
Embodiment 6
The present embodiment anode material for lithium-ion batteries chemical formula is LiNi
0.4co
0.3mn
0.28mg
0.015ti
0.005o
2, its preparation method comprises the following steps:
1) dosing: by Mn (NO
3)
2, Ni (NO
3)
2and Co (NO
3)
22.8:4:3 is made into the first solution in molar ratio, by Mg (NO
3)
2be made into the second solution, EDTA is made into to the 3rd solution, NaOH is made into to the 4th solution;
2) reaction: the method that adopts and flow, by four kinds of solution, be injected in reactor simultaneously, strong stirring, control pH value in whipping process between 10-14, course of reaction is controlled temperature of reaction kettle at 40-70 ℃, after having reacted, and filtration, washing, drying, obtain the hydroxide presoma of Mg Uniform Doped, inert gas or nitrogen protection are arranged in reactor;
3) presoma presintering: by step 2) is at 500 ℃ of presintering 5h, the cooling oxide precursor that obtains;
4) it is powder that the presoma after presintering batch mixing ball milling: by lithium source and step 3) obtained joins ball milling in ball grinder;
5) mixed powder sintering: by step 4) obtained is poured in alumina crucible, then, at 300-700 ℃ of lower sintering 1-10h, continues to be warming up to 800-1200 ℃ of sintering 5-12h, obtains uniform dopant material;
6) powder that coating processing: at first the titanium source is dissolved, then by step 5) sintering obtains joins in titanium solution, stirs, filters and drying, finally at 400-700 ℃ of sintering 2-6h, obtains the blended positive pole material LiNi of desirable titanium coating
0.4co
0.3mn
0.28mg
0.015ti
0.005o
2.
As calculated, the positive electrode LiNi that embodiment 6 makes
0.4co
0.3mn
0.28mg
0.015ti
0.005o
2lithium nickel mixing degree be 1.62%.
Embodiment 7
The chemical formula of the present embodiment anode material for lithium-ion batteries is LiNi
0.5co
0.2mn
0.29ti
0.01o
2, its preparation method comprises the following steps:
1) dosing: by Mn (NO
3)
2, Ni (NO
3)
2and Co (NO
3)
22.9:5:2 is made into the first solution in molar ratio, by TiCl
4be made into the second solution, EDTA is made into to the 3rd solution, NaOH is made into to the 4th solution;
2) reaction: the method that adopts and flow, by four kinds of solution, be injected in reactor simultaneously, strong stirring, control pH value in whipping process between 10-14, course of reaction is controlled temperature of reaction kettle at 40-70 ℃, after having reacted, and filtration, washing, drying, obtain the hydroxide presoma of Ti Uniform Doped, inert gas or nitrogen protection are arranged in reactor;
3) presoma presintering: by step 2) is at 500 ℃ of presintering 5h, the cooling oxide precursor that obtains;
4) it is powder that the presoma after presintering batch mixing ball milling: by lithium source and step 3) obtained joins ball milling in ball grinder;
5) mixed powder sintering: by step 4) obtained is poured in alumina crucible, then, at 300-700 ℃ of lower sintering 1-10h, continues to be warming up to 800-1200 ℃ of sintering 5-12h, obtains uniform dopant material;
6) powder that coating processing: at first the titanium source is dissolved, then by step 5) sintering obtains joins in titanium solution, stirs, filters and drying, finally at 400-700 ℃ of sintering 2-6h, obtains the blended positive pole material LiNi of desirable titanium coating
0.5co
0.2mn
0.29ti
0.01o
2.
As calculated, the positive electrode LiNi that embodiment 7 makes
0.5co
0.2mn
0.29ti
0.01o
2lithium nickel mixing degree be 1.05%.
Comparative Examples 1
The chemical formula of the anode material for lithium-ion batteries that this Comparative Examples provides is LiNi
0.5co
0.2mn
0.3o
2, its preparation method comprises the following steps:
1) dosing: by Mn (NO
3)
2, Ni (NO
3)
2and Co (NO
3)
23:5:2 is made into the first solution in molar ratio, and NaOH is made into to the second solution, and ammoniacal liquor is made into the 3rd solution;
2) reaction: the method that adopts and flow, by four kinds of solution, be injected in reactor simultaneously, strong stirring, control pH value in whipping process between 10-14, course of reaction is controlled temperature of reaction kettle at 40-70 ℃, after having reacted, and filtration, washing, drying, obtain the hydroxide presoma, inert gas or nitrogen protection are arranged in reactor;
3) presoma presintering: by step 2) is at 500 ℃ of presintering 5h, the cooling oxide precursor that obtains;
4) it is powder that the presoma after presintering batch mixing ball milling: by lithium source and step 3) obtained joins ball milling in ball grinder;
5) mixed powder sintering: by step 4) obtained is poured in alumina crucible, then, at 300-700 ℃ of lower sintering 1-10h, continues to be warming up to 800-1200 ℃ of sintering 5-12h, obtains the NCM positive electrode.
As calculated, the positive electrode LiNi that Comparative Examples 1 makes
0.5co
0.2mn
0.3o
2lithium nickel mixing degree be 6.82%.
From the positive electrode Li-Ni mixing degree value of embodiment 1 to 7 and Comparative Examples 1, can find out, the Li-Ni mixing degree value of anode material for lithium-ion batteries of the present invention all is less than 2%, much smaller than the Li-Ni mixing degree of existing positive electrode.
The positive electrode of embodiment 1 to 7 and Comparative Examples 1 is mixed into to anode sizing agent with bonding agent, conductive agent respectively, and this anode sizing agent is coated on plus plate current-collecting body, then through colding pressing, dry and the operation such as cut and make positive plate; The positive plate made is assembled into to lithium ion battery with negative plate, electrolyte and barrier film respectively, and the battery number consecutively be assembled into is S1-S7 and D1.
The lithium ion battery that is numbered S1-S7 and D1 is tested as follows, and test result is as shown in table 1.
Cycle performance test: to being numbered the lithium ion battery of S1-S7 and D1, under 60 ℃, with the rate of charge constant current charge of 0.7C to 4.4V, again with the rate of charge constant voltage charge of 0.05C to 4.4V, then the discharge-rate with 1C is discharged to 3.0V, 400 this charge and discharge cycles repeatedly, measure the discharge capacity of circulation time and the discharge capacity of the 400th circulation time for the first time, obtains the capability retention after circulation; Capability retention after circulation=(discharge capacity of the 400th circulation time)/(discharge capacity of circulation time for the first time) * 100%.
Security performance test: to being numbered the lithium ion battery of S1-S7 and D1, under 25 ℃, with the rate of charge constant current charge of 0.5C to 4.4V, then with the rate of charge constant voltage charge of 0.05C to 4.4V; After standing 1h, battery is put into to convection oven, oven temperature is set as to 30min and is warming up to 150 ℃, and continue baking 6 hours at 150 ℃, with battery in bake process, whether burn and weigh the quality of battery safety.
Table 1: the performance of lithium ion battery test result that is numbered S1-S7 and D1
| The battery numbering | Capability retention after 400 circulations | Whether burn |
| S1 | 82% | No |
| S2 | 81.9% | No |
| S3 | 80% | No |
| S4 | 83% | No |
| S5 | 75% | No |
| S6 | 78% | No |
| S7 | 84% | No |
| D1 | 51% | Be |
From the test result of table 1, can find out: the lithium ion battery that adopts positive electrode of the present invention to prepare experiences 400 Capacitance reserves after circulation and still remains on 80% left and right under the high voltage hot conditions, higher than the capability retention of the battery that is numbered D1, this shows that positive electrode of the present invention can improve the cycle performance of battery under high voltage and hot conditions far away; In addition, under identical test condition, adopt battery prepared by positive electrode of the present invention that combustion phenomena does not occur, illustrate that it has higher security performance.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also carry out suitable change and modification to above-mentioned execution mode.Therefore, the present invention is not limited to embodiment disclosed and described above, to modifications and changes more of the present invention, also should fall in the protection range of claim of the present invention.In addition, although used some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. a polynary stratiform anode material for lithium-ion batteries, is characterized in that, the chemical general formula of described positive electrode is LiNi
am
bn
co
2, Li-Ni mixing degree wherein is less than 2%; In chemical general formula, M is transition metal, and N is one or more in Al, Mg, Ti, Zr, and the value of a, b and c meets a+b+c=1, a>0.3 and c<0.03.
2. polynary stratiform anode material for lithium-ion batteries according to claim 1, is characterized in that, the M in described chemical general formula is one or both in Co, Mn.
3. the preparation method of the described polynary stratiform anode material for lithium-ion batteries of any one in a claim 1 to 2, is characterized in that, comprises the following steps:
1) dosing: the salting liquid of nickel, cobalt, manganese is made into to the first solution, doped metal salt is made into to the second solution, complexing agent is made into to the 3rd solution, aqueous alkali is made into to the 4th solution;
2) four kinds of solution reaction: the method that adopts and flow, by step 1) are injected in reactor simultaneously, and strong stirring, be controlled at pH value between 10-14 in whipping process, and course of reaction control temperature of reaction kettle is at 40-70 ℃; After having reacted, filtration, washing, drying, obtain the hydroxide presoma of metal Uniform Doped;
3) hydroxide presoma presintering: by step 2) obtained is at 400～800 ℃ of lower presintering 2～8h, the cooling oxide precursor that obtains;
4) the oxide precursor ball milling after presintering batch mixing ball milling: by lithium source and step 3) obtained is powder;
5) mixed powder sintering: by step 4) obtained is poured in alumina crucible, then, at 300-700 ℃ of lower sintering 1-10h, continues to be warming up to 800-1200 ℃ of sintering 5-12h, obtains uniform dopant material.
4. the preparation method of polynary stratiform anode material for lithium-ion batteries according to claim 3, it is characterized in that, also comprise step 6) coat and process: will coat presoma and dissolve, by step 5) powder that obtains of sintering joins and coats in precursor solution, stir, filter and drying, finally, at 400-700 ℃ of sintering 2-6h, obtain the blended positive pole material that metal oxide coats.
5. the preparation method of polynary stratiform anode material for lithium-ion batteries according to claim 3, is characterized in that, described step 1) in, manganese salt is Mn (NO
3)
2, MnCl
2, MnSO
4in at least one; Nickel salt is NiCl
2, NiSO
4, Ni (NO
3)
2in at least one; Cobalt salt is CoCl
2, CoSO
4, Co (NO
3)
2in at least one; Doped metal salt is Al salt, Mg salt, Ti salt or Zr salt.
6. the preparation method of polynary stratiform anode material for lithium-ion batteries according to claim 3, is characterized in that, described step 1) in highly basic be NaOH or KOH, complexing agent is ammoniacal liquor or aminocarboxylate.
7. the preparation method of polynary stratiform anode material for lithium-ion batteries according to claim 3, is characterized in that, described step 1) in complexing agent be protein, amino acid or sodium ethylene diamine tetracetate.
8. the preparation method of polynary stratiform anode material for lithium-ion batteries according to claim 3, is characterized in that, described step 2) reactor in inert gas or nitrogen protection are arranged.
9. the preparation method of polynary stratiform anode material for lithium-ion batteries according to claim 3, is characterized in that, described step 3) in duration of ball milling be 3-12h.
10. the preparation method of polynary stratiform anode material for lithium-ion batteries according to claim 3, is characterized in that, described step 4) in the lithium source be LiOH, Li
2o or Li
2cO
3.
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