CN108110253A - Fast-ionic conductor, positive electrode and preparation method thereof by its cladding - Google Patents
Fast-ionic conductor, positive electrode and preparation method thereof by its cladding Download PDFInfo
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- CN108110253A CN108110253A CN201711333226.3A CN201711333226A CN108110253A CN 108110253 A CN108110253 A CN 108110253A CN 201711333226 A CN201711333226 A CN 201711333226A CN 108110253 A CN108110253 A CN 108110253A
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- H01M4/00—Electrodes
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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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- H01M4/50—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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Abstract
The present invention provides one kind by LixMySnzO8New fast-ionic conductor, the positive electrode for lithium ion battery by its cladding represented, the preparation method of the positive electrode for lithium ion battery of the cladding, the anode for lithium ion battery and the lithium ion battery including the anode and/or the fast-ionic conductor as electrolyte prepared by the positive electrode.In LixMySnzO8In, the one kind of M in Mg, Co and Zn, 1<x<2.5,1<y<2.5,2.0<z<3.5.And the positive electrode for lithium ion battery in fast-ionic conductor cladding, wherein, the fast-ionic conductor forms homogeneous clad on the surface of the positive electrode for lithium ion battery, based on the positive electrode that lithium ion battery is used for described in 100 weight %, the amount of the new fast-ionic conductor is 0.1 weight % to 10 weight %.
Description
Technical field
The invention belongs to field of lithium ion secondary, more particularly to a kind of new fast-ionic conductor, the use by its cladding
In the positive electrode of lithium ion battery, the preparation method of the positive electrode for lithium ion battery of the cladding, by the anode material
Expect the anode for lithium ion battery prepared and the lithium ion battery including the anode.
Background technology
Lithium ion battery because high-energy density, high voltage, the long-life, memory-less effect, it is pollution-free the features such as by extensively should
It is following to be led in power battery and large-scale energy storage for portable electronics markets such as cell phone, digital camera, PCs
There is good development prospect in domain.Lithium battery is mainly using liquid electrolyte at present, there are leakage and inflammable, explosive hidden danger,
Cause the safety problem of battery.Replace liquid electrolyte that will greatly improve battery security using solid electrolyte.Fast ion
Conductor has high ionic conductivity, is a kind of preferable solid electrolyte material.
Anode material for lithium-ion batteries is to restrict lithium battery capacity and the key factor in service life, therefore positive electrode is ground
Study carefully and be of great significance.Cobalt acid lithium has capacity high, and tap density is high, and battery energy per volume density is high, comprehensive electrochemistry
Therefore the advantages that function admirable and simple production process, is widely used in the 3C such as smart mobile phone, tablet computer, ultrabook electricity
Sub- product.LiMn2O4, raw material sources are abundant extensively, cheap, and high rate performance is excellent, and technical maturity is usually used in power battery,
But high temperature resistance and cycle performance are bad；Ternary material capacity is high, cycle, but under high voltages using being present with battery appearance
Amount diving phenomenon, cycle performance are poor；LiFePO4 has the preferred material that excellent security is remembered as power battery, but
Since its capacity is low, the reasons such as high rate performance and low temperature performance difference are now mainly used for energy storage field；Nickelic tertiary cathode material
Material great advantage is capacity height, and shortcoming is that the alkalescence of the material is strong, controls requirement harsh battery production environment condition, pole
Big limits promoting the use of for the material.Many results of study show that surface cladding is to improve positive electrode chemical property
Effective ways.Contacting directly for positive electrode and electrolyte can be prevented by surface coating modification, inhibit the generation of side reaction,
Promote the cycle performance of positive electrode；Secondly, high conductivity material can increase positive electrode electronic conductivity or ionic conductance
Rate promotes the high rate performance of material.
The content of the invention
Technical problem
In order to solve the problems, such as present in positive electrode of the prior art, the present inventor is by largely grinding
Study carefully a kind of creative new fast-ionic conductor of discovery.When the positive electrode by ion conductor cladding for lithium ion battery
When, charge transfer resistance of the battery in charge and discharge process can be reduced, significantly improve positive electrode high rate capability and
Cyclical stability, and the interface membrane impedance and Charge-transfer resistance of electrolyte and positive electrode are effectively improved, and significantly
Improve Xun Huan and high rate performance, while the fast-ionic conductor is also used as the solid electrolyte of lithium ion battery.
Technical solution
The object of the present invention is to provide a kind of fast-ionic conductor, by the fast-ionic conductor coat for lithium ion battery
Positive electrode, the preparation method of the positive electrode for lithium ion battery of the cladding, the anode prepared by the positive electrode, with
And the lithium ion battery comprising the anode.
According to an aspect of the invention, there is provided a kind of fast-ionic conductor, by LixMySnzO8It represents, wherein M is selected from
One kind in Mg, Co and Zn, 1<x<2.5,1<y<2.5,2.0<z<3.5.
Preferably, the fast-ionic conductor is Li1.6Mg1.6Sn2.8O8、Li1.4Co1.4Sn2.6O8Or Li1.6Zn1.6Sn2.8O8。
According to another aspect of the present invention, the preparation method of the fast-ionic conductor is provided, is included the following steps：
(1) stoichiometrically lithium salts, M salt, pink salt are dissolved in deionized water or alcohol, are optionally added into acid, stirring is extremely
It is completely dissolved；
(2) aqueous slkali is added dropwise into the solution that step (1) obtains and adjusts pH value to 8.0~10.0, obtains containing hydroxide
The suspension of object precipitation, filters and dries；
(3) by the powder mull of gained in step (2), then under conditions of air, calcining heat is at 500~950 DEG C, 3
~5 DEG C/min heats up, and calcines 2-12h, obtains the fast-ionic conductor,
The M salt is selected from magnesium salts, cobalt salt and zinc salt.
The alcohol is alcohol commonly used in the art, is preferably selected from methanol, ethyl alcohol, propyl alcohol, isopropanol and butanol.
The aqueous slkali is can be so as to the aqueous solution that adjusting solution ph is 8.0-10.0, includes, but not limited to ammonia
Aqueous solution, sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate and potassium bicarbonate aqueous solution etc. are preferably, ammonia
Aqueous solution.
The lithium salts is selected from lithium carbonate, lithium nitrate, lithium hydroxide or lithium acetate.
The magnesium salts is selected from magnesium nitrate, magnesium chloride, magnesium acetate, magnesium citrate or magnesium ethylate.
The cobalt salt is selected from cobalt acetate, cobalt nitrate or cobaltous sulfate.
The zinc salt is selected from zinc acetate, zinc nitrate, zinc chloride or zinc sulfate.
The pink salt is selected from stannic chloride, stannous chloride, stannous sulfate, nitric acid tin, nitric acid stannous or tin acetate.
Object is closed since partial lithiation in calcination process, can be vapored away, so general excessive 3 moles of %~10 of lithium are rubbed
You are %.That is, the lithium ion in solution in step (1)：M ions：The molar ratio of tin ion is (1.03~1.1) x：y：z.
It is to form the solution for including each ion to add in acid in step (1), and the acid is not particularly limited, example bag
It includes, but is not limited to, hydrochloric acid, nitric acid, sulfuric acid, acetic acid etc..
According to another aspect of the present invention, the anode material for lithium ion battery of the fast-ionic conductor cladding is provided
Material, the fast-ionic conductor form homogeneous clad on the surface of the positive electrode, wherein, the fast-ionic conductor is
LixMySnzO8, the one kind of wherein M in Mg, Co and Zn, 1<x<2.5,1<y<2.5,2.0<z<3.5, based on 100 weight %
Positive electrode, the amount of the new fast-ionic conductor is 0.1 weight % to 10 weight %, preferably 0.2 weight % to 6 weights
Measure %, more preferable 0.5 weight % to 3 weight %.
The positive electrode for lithium ion battery is graininess or stratiform, and selected from LiCoO2；LiNi0.5Mn1.5O4；
LiNi0.8Co0.15Al0.05O2；LiNiaCo1-aO2, wherein, 0 ＜ a ＜ 1；LiNibCocMn1-b-cO2, wherein, 0 ＜ b ＜, 1,0 ＜ c ＜
1；And Li2MnO3·LiNidCoeMn1-d-eO2, wherein 0 ＜ d ＜, 1,0 ＜ e ＜ 1.
According to another aspect of the present invention, provide it is a kind of prepare the new fast-ionic conductor cladding for lithium from
The method of the positive electrode of sub- battery, described method includes following steps：
(1) stoichiometrically lithium salts, M salt, pink salt are dissolved in deionized water or alcohol, are optionally added into acid, stirring is extremely
It is completely dissolved；
(2) aqueous slkali is added dropwise into the solution that step (1) obtains and adjusts pH value to 8.0~10.0, obtains containing hydroxide
The suspension of object precipitation；
(3) positive electrode that lithium battery is used for described in graininess or stratiform is added in the suspension obtained by step (2),
Stirring, is then dried；
(4) by the powder mull of gained in step (3), then under conditions of air, calcining heat is at 500~950 DEG C, 3
~5 DEG C/min heats up, and calcines 2-12h, can obtain the positive electrode for lithium ion battery of fast-ionic conductor cladding；
Wherein, in the positive electrode coated in the new fast-ionic conductor of gained, based on the positive electrode of 100 weight %,
The amount of the new fast-ionic conductor is 0.1 weight % to 10 weight %, preferably 0.2 weight % to 6 weight %, more preferable 0.5
Weight % to 3 weight %；
The M salt is selected from magnesium salts, cobalt salt and zinc salt.
The concentration of metal ions of metal salt (such as lithium salts, the M salt and pink salt) solution can be 0.001M-0.020M,
It is preferred that 0.005M-0.01M.If concentration in this scope, will not cause to be difficult to be evenly coated.
The lithium salts is selected from lithium carbonate, lithium nitrate, lithium hydroxide or lithium acetate.
The magnesium salts is selected from magnesium nitrate, magnesium chloride, magnesium acetate, magnesium citrate or magnesium ethylate.
The cobalt salt is selected from cobalt acetate, cobalt nitrate or cobaltous sulfate.
The zinc salt is selected from zinc acetate, zinc nitrate, zinc chloride or zinc sulfate.
The pink salt is selected from stannic chloride, stannous chloride, stannous sulfate, nitric acid tin, nitric acid stannous or tin acetate.
The aqueous slkali is can be so as to the aqueous solution that adjusting solution ph is 8.0-10.0, includes, but not limited to ammonia
Aqueous solution, sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate and potassium bicarbonate aqueous solution etc..
The positive electrode is selected from LiCoO2；LiNi0.5Mn1.5O4；LiNi0.8Co0.15Al0.05O2；LiNiaCo1-aO2, wherein
0 ＜ a ＜ 1；LiNibCocMn1-b-cO2, wherein, 0 ＜ b ＜, 1,0 ＜ c ＜ 1；And Li2MnO3·LiNidCoeMn1-d-eO2, wherein, 0
1,0 ＜ e ＜ 1 of ＜ d ＜.The positive electrode is usually graininess or stratified material, in the case that be granular, granularity D50
For 2 to 20 microns, preferably 3 to 15 microns, more preferable 6 to 10 microns.
Object is closed since partial lithiation in calcination process, can be vapored away, so general excessive 3 moles of %~10 of lithium are rubbed
You are %.That is, the lithium ion in solution in step (1)：M ions：The molar ratio of tin ion is (1.03~1.1) x：y：z.
It is to form the solution for including each ion to add in acid in step (1), and the acid is not particularly limited, example bag
It includes, but is not limited to, hydrochloric acid, nitric acid, sulfuric acid, acetic acid etc..
According to another aspect of the invention, the anode for lithium ion battery is provided, it includes of the present invention new
The positive electrode of type fast-ionic conductor cladding.
According to another aspect of the present invention, use of the fast-ionic conductor as the electrolyte of lithium ion battery is provided
On the way.
In accordance with a further aspect of the present invention, provide a kind of lithium ion battery, including the anode and/or it is described soon from
Sub- conductor is as electrolyte.
Advantageous effect
1st, the present invention mainly utilizes fast-ionic conductor LixMySnzO8(one kind of M in Mg, Co and Zn, 1<X 2.5,
1<y<2.5,2.0<z<3.5) the shortcomings that replacing liquid electrolyte that can overcome also liquid electrolyte leakage and easily burning, significantly
Improve battery security.
2nd, the present invention is mainly coated on positive electrode surface using the fast-ionic conductor, reduces positive electrode and electrolysis
Liquid contacts, and electrolyte is reduced to the erosion of positive electrode and the dissolution of metallic element, so as to better cycle performance；
Secondly fine and close homogeneous clad is formed in surface of active material, it is suppressed that the reaction of electrolyte and electrode active material is dropped
The low interface resistance of electrolyte and electrode material.
3rd, fast-ionic conductor of the present invention have high ionic conductivity, be coated on positive electrode can strengthen lithium from
Son transfers between solid state electrode and electrolyte, reduces charge transfer resistance of the battery in charge and discharge process, therefore not only
The cyclical stability of positive electrode can be improved but also the high rate performance of positive electrode can be significantly improved.
Description of the drawings
Fig. 1 is the Li according to the embodiment of the present invention 11.6Mg1.6Sn2.8O8XRD diagram.
Fig. 2 is according to coating 1.5 weight %Li in the embodiment of the present invention 51.4Co1.4Sn2.6O8Cobalt acid lithium material and basis
The cycle performance comparison diagram of the uncoated cobalt acid lithium material of comparative example 2.
Fig. 3 is the discharge curve under different multiplying according to the uncoated cobalt acid lithium material of comparative example 2.
Fig. 4 is to coat 1.5 weight %Li in the embodiment of the present invention 51.4Co1.4Sn2.6O8Cobalt acid lithium material in different multiplying
Under discharge curve.
Specific embodiment
In order to there is deeper understanding to the present invention, technical solution is clearly and completely described with reference to embodiment,
But the embodiment of present aspect, just for the sake of explaining the present invention, not limitation is of the invention.
Embodiment 1
1) solid electrolyte Li1.6Mg1.6Sn2.8O8Preparation
It is 4.2 in molar ratio:4:7 lithium hydroxides weighed respectively, magnesium nitrate, tin acetate are dissolved in the deionized water of 200ml
In, 2-3h is at the uniform velocity stirred, ammonium hydroxide is added dropwise under conditions of being stirred continuously until completely dissolved, pH value is adjusted to after 8.0-10.0
Stirring is evaporated under conditions of 80 DEG C, afterwards in 80 DEG C of dry 12h of air dry oven, 950 DEG C of calcinings in air atmosphere after grinding
12h can obtain Li1.6Mg1.6Sn2.8O8Powder, then powder is taken to be pressed into piece.
2) ionic conductivity is tested
The Li after piece will be pressed into1.6Mg1.6Sn2.8O8Solid electrolyte is clipped among two panels stainless steel, is assembled into battery, from
Electron conductivity is measured using electrochemical alternate impedance spectrum, using formula σ=d/RbA, wherein d are the thickness of solid electrolyte
Degree, A are electrode area RbFor the impedance measured, ionic conductivity of the electrolyte at 25 DEG C is obtained after calculating as 1.9210-11s·cm-1。
3) electrochemical property test
Anode：With LiCoO2For active material, SP is conductive agent, and PVDF is binding agent, n-methyl-2-pyrrolidone
(NMP) it is dispersant, by LiCoO2：SP：PVDF=84：8：8 weight ratio is sized mixing, and is applied on aluminium foil and is made electrode slice.With gold
Belong to lithium piece as cathode, positive and negative anodes clamp the Li after being pressed into piece1.6Mg1.6Sn2.8O8Solid electrolyte, in the gloves full of argon gas
Button half-cell is made in case.Electro-chemical test is carried out at normal temperatures, and charge and discharge blanking voltage is 3.0V-4.5V.Wherein, for the first time
The specific discharge capacity under capacity retention ratio and 10C after specific discharge capacity, 80 circle of 1C Xun Huans refers to table 1.
Embodiment 2
1) solid electrolyte Li1.4Co1.4Sn2.6O8Preparation
It is 1.47 in molar ratio:1.4:2.6 lithium hydroxides weighed respectively, cobalt nitrate, tin acetate be dissolved in 200ml go from
In sub- water, 2-3h is at the uniform velocity stirred, ammonium hydroxide is added dropwise under conditions of being stirred continuously until completely dissolved, pH value is adjusted to 8.0-10.0
It stirs and is evaporated under conditions of 80 DEG C afterwards, afterwards in 80 DEG C of dry 12h of air dry oven, 950 DEG C in air atmosphere after grinding
Calcining 12h can obtain Li1.4Co1.4Sn2.6O8Powder, then powder is taken to be pressed into piece.
2) ionic conductivity is tested
The Li after piece will be pressed into1.4Co1.4Sn2.6O8Solid electrolyte is clipped among two panels stainless steel, is assembled into battery, from
Electron conductivity is measured using electrochemical alternate impedance spectrum, using formula σ=d/RbA, wherein d are the thickness of solid electrolyte
Degree, A are electrode area RbFor the impedance measured, ionic conductivity of the electrolyte at 25 DEG C is obtained after calculating as 3.6410-11s·cm-1。
3) electrochemical property test
Anode：With LiCoO2For active material, SP is conductive agent, and PVDF is binding agent, n-methyl-2-pyrrolidone
(NMP) it is dispersant, by LiCoO2：SP：PVDF=84：8：8 mass ratio is sized mixing, and is applied on aluminium foil and is made electrode slice.With gold
Belong to lithium piece as cathode, positive and negative anodes clamp the Li after being pressed into piece1.4Co1.4Sn2.6O8Solid electrolyte, in the gloves full of argon gas
Button half-cell is made in case.Electro-chemical test is carried out at normal temperatures, and charge and discharge blanking voltage is 3.0V-4.5V.Wherein, for the first time
The specific discharge capacity under capacity retention ratio and 10C after specific discharge capacity, 80 circle of 1C Xun Huans refers to table 1.
Embodiment 3
1) solid electrolyte Li1.6Zn1.6Sn2.8O8Preparation
It is 4.2 in molar ratio:4:7 weigh lithium hydroxide, zinc nitrate, tin acetate respectively is dissolved in the deionized water of 200ml,
2-3h is at the uniform velocity stirred, ammonium hydroxide is added dropwise under conditions of being stirred continuously until completely dissolved, pH value is adjusted to after 8.0-10.0 80
Stirring is evaporated under conditions of DEG C, afterwards in 80 DEG C of dry 12h of air dry oven, after grinding in air atmosphere 950 DEG C calcine 12h
It can obtain Li1.6Zn1.6Sn2.8O8Powder, then powder is taken to be pressed into piece.
2) ionic conductivity is tested
The Li after piece will be pressed into1.6Zn1.6Sn2.8O8Solid electrolyte is clipped among two panels stainless steel, is assembled into battery, from
Electron conductivity is measured using electrochemical alternate impedance spectrum, using formula σ=d/RbA, wherein d are the thickness of solid electrolyte
Degree, A are electrode area RbFor the impedance measured, ionic conductivity of the electrolyte at 25 DEG C is obtained after calculating as 1.8810-11s·cm-1。
3) electrochemical property test
Anode：With LiCoO2For active material, SP is conductive agent, and PVDF is binding agent, n-methyl-2-pyrrolidone
(NMP) it is dispersant, by LiCoO2：SP：PVDF=84：8：8 mass ratio is sized mixing, and is applied on aluminium foil and is made electrode slice.With gold
Belong to lithium piece as cathode, positive and negative anodes clamp the Li after being pressed into piece1.6Zn1.6Sn2.8O8Solid electrolyte, in the gloves full of argon gas
Button half-cell is made in case.Electro-chemical test is carried out at normal temperatures, and charge and discharge blanking voltage is 3.0V-4.5V.Wherein, for the first time
The specific discharge capacity under capacity retention ratio and 10C after specific discharge capacity, 80 circle of 1C Xun Huans refers to table 1.
Comparative example 1
1) solid electrolyte Li2SnO3Preparation
It is 2.1 in molar ratio:1 weighs lithium hydroxide respectively, tin acetate is dissolved in the deionized water of 200ml, at the uniform velocity stirs
Ammonium hydroxide is added dropwise in 2-3h under conditions of being stirred continuously until completely dissolved, and pH value is adjusted to after 8.0-10.0 in 80 DEG C of condition
Lower stirring is evaporated, and afterwards in 80 DEG C of dry 12h of air dry oven, 950 DEG C of calcining 12h can be obtained in air atmosphere after grinding
Li2SnO3Powder, then powder is taken to be pressed into piece.
2) ionic conductivity is tested
The Li after piece will be pressed into2SnO3Solid electrolyte is clipped among two panels stainless steel, is assembled into battery, ionic conductivity
It is measured using electrochemical alternate impedance spectrum, using formula σ=d/RbA, wherein d are the thickness of solid electrolyte, and A is electrode
Area RbFor the impedance measured, ionic conductivity of the electrolyte at 25 DEG C is obtained after calculating as 6.2810-13s·cm-1。
3) electrochemical property test
Anode：With LiCoO2For active material, SP is conductive agent, and PVDF is binding agent, n-methyl-2-pyrrolidone
(NMP) it is dispersant, by LiCoO2：SP：PVDF=84：8：8 mass ratio is sized mixing, and is applied on aluminium foil and is made electrode slice.With gold
Belong to lithium piece as cathode, positive and negative anodes clamp the Li after being pressed into piece2SnO3Solid electrolyte makes in the glove box full of argon gas
Button half-cell.Electro-chemical test is carried out at normal temperatures, and charge and discharge blanking voltage is 3.0V-4.5V.Wherein, discharge specific volume for the first time
The specific discharge capacity under capacity retention ratio and 10C after amount, 80 circle of 1C Xun Huans refers to table 1.
Embodiment 4
1) 1.5 weight %Li1.6Mg1.6Sn2.8O8The preparation of the cobalt acid lithium of cladding
It is 4.2 in molar ratio:4:7 weigh lithium hydroxide, magnesium nitrate, tin acetate respectively is dissolved in the deionized water of 150ml,
2-3h is at the uniform velocity stirred, ammonium hydroxide is added dropwise under conditions of being stirred continuously until completely dissolved, is added in after pH value is adjusted to 8.0-10.0
The cobalt acid lithium commodity powder of corrresponding quality, then stirs under conditions of 80 DEG C and is evaporated, afterwards in 80 DEG C of dryings of air dry oven
12h, 850 DEG C of calcining 3h can obtain Li in air atmosphere after grinding1.6Mg1.6Sn2.8O8The lithium-ion electric of the cobalt acid lithium of cladding
Pond positive electrode.
2) electrochemical property test
Anode：With Li1.6Mg1.6Sn2.8O8The LiCoO of cladding2For active material, SP is conductive agent, and PVDF is binding agent, N-
N-methyl-2-2-pyrrolidone N (NMP) is dispersant, by LiCoO2：SP：PVDF=84：8：8 mass ratio is sized mixing, and is applied on aluminium foil
Make electrode slice.Using metal lithium sheet as cathode, with polyethylene (PE) for membrane, button is made in the glove box full of argon gas
Half-cell.Wherein polyethene microporous membrane is membrane, and half-cell is lithium piece to electrode.Electro-chemical test is carried out at normal temperatures, is filled
Discharge cut-off voltage is 3.0V-4.5V.Wherein, under the capacity retention ratio and 10C after first discharge specific capacity, 80 circle of 1C Xun Huans
Specific discharge capacity refers to table 1.
Embodiment 5
1) 1.5 weight %Li1.4Co1.4Sn2.6O8The preparation of the cobalt acid lithium of cladding
It is 1.47 in molar ratio:1.4:2.6 weigh the deionization that lithium hydroxide, cobalt nitrate, tin acetate are dissolved in 150ml respectively
In water, 2-3h is at the uniform velocity stirred, ammonium hydroxide is added dropwise under conditions of being stirred continuously until completely dissolved, after pH value is adjusted to 8.0-10.0
The cobalt acid lithium commodity powder of corrresponding quality is added in, then stirs and is evaporated under conditions of 80 DEG C, it is dry in 80 DEG C of air dry oven afterwards
Dry 12h, 750 DEG C of calcining 3h can obtain Li in air atmosphere after grinding1.4Co1.4Sn2.6O8The lithium ion of the cobalt acid lithium of cladding
Cell positive material.
2) electrochemical property test
Anode：With Li1.4Co1.4Sn2.6O8The LiCoO of cladding2For active material, SP is conductive agent, and PVDF is binding agent, N-
N-methyl-2-2-pyrrolidone N (NMP) is dispersant, by LiCoO2：SP：PVDF=84：8：8 mass ratio is sized mixing, and is applied on aluminium foil
Make electrode slice.Using metal lithium sheet as cathode, with polyethylene (PE) for membrane, button is made in the glove box full of argon gas
Half-cell.Wherein polyethene microporous membrane is membrane, and half-cell is lithium piece to electrode.Electro-chemical test is carried out at normal temperatures, is filled
Discharge cut-off voltage is 3.0V-4.5V.Wherein, under the capacity retention ratio and 10C after first discharge specific capacity, 80 circle of 1C Xun Huans
Specific discharge capacity refers to table 1.
Embodiment 6
1) 1.5 weight %Li1.6Zn1.6Sn2.8O8The preparation of the cobalt acid lithium of cladding
It is 4.2 in molar ratio:4:7 weigh lithium hydroxide, zinc nitrate, tin acetate respectively is dissolved in the deionized water of 150ml,
2-3h is at the uniform velocity stirred, ammonium hydroxide is added dropwise under conditions of being stirred continuously until completely dissolved, is added in after pH value is adjusted to 8.0-10.0
The cobalt acid lithium commodity powder of corrresponding quality, then stirs under conditions of 80 DEG C and is evaporated, afterwards in 80 DEG C of dryings of air dry oven
12h, 900 DEG C of calcining 3h can obtain Li in air atmosphere after grinding1.6Zn1.6Sn2.8O8The lithium-ion electric of the cobalt acid lithium of cladding
Pond positive electrode.
2) electrochemical property test
Anode：With Li1.6Zn1.6Sn2.8O8The LiCoO of cladding2For active material, SP is conductive agent, and PVDF is binding agent, N-
N-methyl-2-2-pyrrolidone N (NMP) is dispersant, by LiCoO2：SP：PVDF=84：8：8 mass ratio is sized mixing, and is applied on aluminium foil
Make electrode slice.Using metal lithium sheet as cathode, with polyethylene (PE) for membrane, button is made in the glove box full of argon gas
Half-cell.Wherein polyethene microporous membrane is membrane, and half-cell is lithium piece to electrode.Electro-chemical test is carried out at normal temperatures, is filled
Discharge cut-off voltage is 3.0V-4.5V.Wherein, under the capacity retention ratio and 10C after first discharge specific capacity, 80 circle of 1C Xun Huans
Specific discharge capacity refers to table 1.
Comparative example 2
Except active material is uncoated LiCoO in positive plate2Outside, it is prepared according to step same as Example 4
Lithium ion battery and test chemical property.Wherein, the capacity retention ratio and 10C after first discharge specific capacity, 80 circle of 1C Xun Huans
Under specific discharge capacity refer to table 1.
Embodiment 7
1) 1.0 weight %Li1.6Mg1.6Sn2.8O8Coat ternary material LiNi0.6Co0.2Mn0.2O2Preparation
Take commodity presoma Ni0.6Co0.2Mn0.2(OH)21 is pressed with LiOH：1.05 mixed in molar ratio, 550 DEG C under air
Pre-burning 4h, after grinding again under air 820 DEG C calcining 12h after obtain ternary material LiNi0.6Co0.2Mn0.2O2.It is in molar ratio
4.2:4:7 weigh lithium hydroxide, magnesium nitrate, tin acetate respectively is dissolved in the deionized water of 150ml, at the uniform velocity stirs 2-3h, has treated
Ammonium hydroxide is added dropwise after fully dissolved under conditions of being stirred continuously, corrresponding quality is added in after pH value is adjusted to 8.0-10.0
LiNi0.6Co0.2Mn0.2O2, then stir and be evaporated under conditions of 80 DEG C, afterwards in 80 DEG C of dry 12h of air dry oven, grinding
850 DEG C of calcining 3h can obtain Li in air atmosphere afterwards1.6Mg1.6Sn2.8O8The ternary cathode material of lithium ion battery of cladding.
2) electrochemical property test
Anode：With Li1.6Mg1.6Sn2.8O8The LiNi of cladding0.6Co0.2Mn0.2O2For active material, AB is conductive agent, PVDF
For binding agent, n-methyl-2-pyrrolidone (NMP) is dispersant, by LiNi0.6Co0.2Mn0.2O2：AB：PVDF=8：1：1 matter
Amount ratio is sized mixing, and is applied on aluminium foil and is made electrode slice.Using metal lithium sheet as cathode, with polyethylene (PE) for membrane, full of argon
Button half-cell is made in the glove box of gas.Wherein polyethene microporous membrane is membrane, and half-cell is lithium piece to electrode.In room temperature
Lower carry out electro-chemical test, charge and discharge blanking voltage are 3.0V-4.6V.Wherein, after first discharge specific capacity, 80 circle of 1C Xun Huans
Specific discharge capacity under capacity retention ratio and 10C refers to table 1.
Embodiment 8
1) 1.0 weight %Li1.4Co1.4Sn2.6O8Coat ternary material LiNi0.6Co0.2Mn0.2O2Preparation
Take commodity presoma Ni0.6Co0.2Mn0.2(OH)21 is pressed with LiOH：1.05 mixed in molar ratio, 550 DEG C under air
Pre-burning 4h, after grinding again under air 820 DEG C calcining 12h after obtain ternary material LiNi0.6Co0.2Mn0.2O2.It is in molar ratio
1.47:1.4:2.6 weigh lithium hydroxide, cobalt nitrate, tin acetate respectively is dissolved in the deionized water of 150ml, at the uniform velocity stirs 2-3h,
Ammonium hydroxide is added dropwise under conditions of being stirred continuously until completely dissolved, corrresponding quality is added in after pH value is adjusted to 8.0-10.0
LiNi0.6Co0.2Mn0.2O2, then stir and be evaporated under conditions of 80 DEG C, afterwards in 80 DEG C of dry 12h of air dry oven, grinding
750 DEG C of calcining 3h can obtain Li in air atmosphere afterwards1.4Co1.4Sn2.6O8The ternary cathode material of lithium ion battery of cladding.
2) electrochemical property test
Anode：With Li1.4Co1.4Sn2.6O8The LiNi of cladding0.6Co0.2Mn0.2O2For active material, AB is conductive agent, PVDF
For binding agent, n-methyl-2-pyrrolidone (NMP) is dispersant, by LiNi0.6Co0.2Mn0.2O2：AB：PVDF=8：1：1 matter
Amount ratio is sized mixing, and is applied on aluminium foil and is made electrode slice.Using metal lithium sheet as cathode, with polyethylene (PE) for membrane, full of argon
Button half-cell is made in the glove box of gas.Wherein polyethene microporous membrane is membrane, and half-cell is lithium piece to electrode.In room temperature
Lower carry out electro-chemical test, charge and discharge blanking voltage are 3.0V-4.6V.Wherein, after first discharge specific capacity, 80 circle of 1C Xun Huans
Specific discharge capacity under capacity retention ratio and 10C refers to table 1.
Embodiment 9
1) 1.0 weight %Li1.6Zn1.6Sn2.8O8Coat ternary material LiNi0.6Co0.2Mn0.2O2Preparation
Take commodity presoma Ni0.6Co0.2Mn0.2(OH)21 is pressed with LiOH：1.05 mixed in molar ratio, 550 DEG C under air
Pre-burning 4h, after grinding again under air 820 DEG C calcining 12h after obtain ternary material LiNi0.6Co0.2Mn0.2O2.It is in molar ratio
4.2:4:7 weigh lithium hydroxide, zinc nitrate, tin acetate respectively is dissolved in the deionized water of 150ml, at the uniform velocity stirs 2-3h, has treated
Ammonium hydroxide is added dropwise after fully dissolved under conditions of being stirred continuously, corrresponding quality is added in after pH value is adjusted to 8.0-10.0
LiNi0.6Co0.2Mn0.2O2, then stir and be evaporated under conditions of 80 DEG C, afterwards in 80 DEG C of dry 12h of air dry oven, grinding
900 DEG C of calcining 3h can obtain Li in air atmosphere afterwards1.6Zn1.6Sn2.8O8The ternary cathode material of lithium ion battery of cladding.
2) electrochemical property test
Anode：With Li1.6Zn1.6Sn2.8O8The LiNi of cladding0.6Co0.2Mn0.2O2For active material, AB is conductive agent, PVDF
For binding agent, n-methyl-2-pyrrolidone (NMP) is dispersant, by LiNi0.6Co0.2Mn0.2O2：AB：PVDF=8：1：1 matter
Amount ratio is sized mixing, and is applied on aluminium foil and is made electrode slice.Using metal lithium sheet as cathode, with polyethylene (PE) for membrane, full of argon
Button half-cell is made in the glove box of gas.Wherein polyethene microporous membrane is membrane, and half-cell is lithium piece to electrode.In room temperature
Lower carry out electro-chemical test, charge and discharge blanking voltage are 3.0V-4.6V.Wherein, after first discharge specific capacity, 80 circle of 1C Xun Huans
Specific discharge capacity under capacity retention ratio and 10C refers to table 1.
Comparative example 3
Except active material is uncoated ternary material LiNi in positive plate0.6Co0.2Mn0.2O2Outside, according to implementation
The identical step of example 7 prepares lithium ion battery and test chemical property.Wherein, after first discharge specific capacity, 80 circle of 1C Xun Huans
Capacity retention ratio and 10C under specific discharge capacity refer to table 1.
Embodiment 10
1) 1.5 weight %Li1.6Mg1.6Sn2.8O8Coat lithium-rich positive electrode Li1.2Ni0.2Mn0.6O2Preparation
Take 6.4273g LiCH3COO·2H2O, 2.4884g Ni (CH3COO)2·2H2O, 7.3527g Mn
(CH3COO)2·4H2O, 8.4056g citric acid are dissolved in 100ml water, stirring be completely dissolved after be put into micro-wave oven, in low fire
Heat 20 minutes and be evaporated, will under 500 DEG C obtained of gel abrasive (1 DEG C/min heatings) reaction 5 it is small when, after secondary grinding
900 DEG C of sintering 10h obtain rich lithium material.It is 4.2 in molar ratio:4:7 weigh lithium hydroxide, magnesium nitrate, tin acetate respectively is dissolved in
In the deionized water of 150ml, 2-3h is at the uniform velocity stirred, ammonium hydroxide is added dropwise under conditions of being stirred continuously until completely dissolved, by pH value
It is adjusted to add in after 8.0-10.0 the Li of corrresponding quality1.2Ni0.2Mn0.6O2, it then stirs and is evaporated under conditions of 80 DEG C, Zhi Hou
The dry 12h of 80 DEG C of air dry oven, 850 DEG C of calcining 3h can obtain Li in air atmosphere after grinding1.6Mg1.6Sn2.8O8Cladding
Lithium ion lithium-rich anode material.
2) electrochemical property test
Anode：With Li1.6Mg1.6Sn2.8O8The Li of cladding1.2Ni0.2Mn0.6O2For active material, AB is conductive agent, and PVDF is
Binding agent, n-methyl-2-pyrrolidone (NMP) is dispersant, by Li1.2Ni0.2Mn0.6O2：AB：PVDF=8：1：1 mass ratio
It sizes mixing, is applied on aluminium foil and makes electrode slice.Using metal lithium sheet as cathode, with polyethylene (PE) for membrane, full of argon gas
Button half-cell is made in glove box.Wherein polyethene microporous membrane is membrane, and half-cell is lithium piece to electrode.At normal temperatures into
Row electro-chemical test, charge and discharge blanking voltage are 2.0V-4.8V.Wherein, the capacity after first discharge specific capacity, 80 circle of 1C Xun Huans
Specific discharge capacity under conservation rate and 10C refers to table 1.
Embodiment 11
1) 1.5 weight %Li1.4Co1.4Sn2.6O8Coat lithium-rich positive electrode Li1.2Ni0.2Mn0.6O2Preparation
Take 6.4273g LiCH3COO·2H2O, 2.4884g Ni (CH3COO)2·2H2O, 7.3527g Mn
(CH3COO)2·4H2O, 8.4056g citric acid are dissolved in 100ml water, stirring be completely dissolved after be put into micro-wave oven, in low fire
Heat 20 minutes and be evaporated, will under 500 DEG C obtained of gel abrasive (1 DEG C/min heatings) reaction 5 it is small when, after secondary grinding
900 DEG C of sintering 10h obtain rich lithium material.It is 1.47 in molar ratio:1.4:2.6 weigh lithium hydroxide, cobalt nitrate, tin acetate respectively
It is dissolved in the deionized water of 150ml, at the uniform velocity stirs 2-3h, ammonium hydroxide is added dropwise under conditions of being stirred continuously until completely dissolved, it will
PH value is adjusted to the Li of addition corrresponding quality after 8.0-10.01.2Ni0.2Mn0.6O2, it then stirs and is evaporated under conditions of 80 DEG C, it
Afterwards in 80 DEG C of dry 12h of air dry oven, 750 DEG C of calcining 3h can obtain Li in air atmosphere after grinding1.4Co1.4Sn2.6O8
The lithium ion lithium-rich anode material of cladding.
2) electrochemical property test
Anode：With Li1.4Co1.4Sn2.6O8The Li of cladding1.2Ni0.2Mn0.6O2For active material, AB is conductive agent, and PVDF is
Binding agent, n-methyl-2-pyrrolidone (NMP) is dispersant, by Li1.2Ni0.2Mn0.6O2：AB：PVDF=8：1：1 mass ratio
It sizes mixing, is applied on aluminium foil and makes electrode slice.Using metal lithium sheet as cathode, with polyethylene (PE) for membrane, full of argon gas
Button half-cell is made in glove box.Wherein polyethene microporous membrane is membrane, and half-cell is lithium piece to electrode.At normal temperatures into
Row electro-chemical test, charge and discharge blanking voltage are 2.0V-4.8V.Wherein, the capacity after first discharge specific capacity, 80 circle of 1C Xun Huans
Specific discharge capacity under conservation rate and 10C refers to table 1.
Embodiment 12
1) 1.5 weight %Li1.6Zn1.6Sn2.8O8Coat lithium-rich positive electrode Li1.2Ni0.2Mn0.6O2Preparation
Take 6.4273g LiCH3COO·2H2O, 2.4884g Ni (CH3COO)2·2H2O, 7.3527g Mn
(CH3COO)2·4H2O, 8.4056g citric acid are dissolved in 100ml water, stirring be completely dissolved after be put into micro-wave oven, in low fire
Heat 20 minutes and be evaporated, will under 500 DEG C obtained of gel abrasive (1 DEG C/min heatings) reaction 5 it is small when, after secondary grinding
900 DEG C of sintering 10h obtain rich lithium material.It is 4.2 in molar ratio:4:7 weigh lithium hydroxide, zinc nitrate, tin acetate respectively is dissolved in
In the deionized water of 150ml, 2-3h is at the uniform velocity stirred, ammonium hydroxide is added dropwise under conditions of being stirred continuously until completely dissolved, by pH value
It is adjusted to add in after 8.0-10.0 the Li of corrresponding quality1.2Ni0.2Mn0.6O2, it then stirs and is evaporated under conditions of 80 DEG C, Zhi Hou
The dry 12h of 80 DEG C of air dry oven, 900 DEG C of calcining 3h can obtain Li in air atmosphere after grinding1.6Zn1.6Sn2.8O8Cladding
Lithium ion lithium-rich anode material.
2) electrochemical property test
Anode：With Li1.6Zn1.6Sn2.8O8The Li of cladding1.2Ni0.2Mn0.6O2For active material, AB is conductive agent, and PVDF is
Binding agent, n-methyl-2-pyrrolidone (NMP) is dispersant, by Li1.2Ni0.2Mn0.6O2：AB：PVDF=8：1：1 mass ratio
It sizes mixing, is applied on aluminium foil and makes electrode slice.Using metal lithium sheet as cathode, with polyethylene (PE) for membrane, full of argon gas
Button half-cell is made in glove box.Wherein polyethene microporous membrane is membrane, and half-cell is lithium piece to electrode.At normal temperatures into
Row electro-chemical test, charge and discharge blanking voltage are 2.0V-4.8V.Wherein, the capacity after first discharge specific capacity, 80 circle of 1C Xun Huans
Specific discharge capacity under conservation rate and 10C refers to table 1
Comparative example 4
Except active material is uncoated lithium-rich positive electrode Li in positive plate1.2Ni0.2Mn0.6O2Outside, according to
Step same as in Example 10 prepares lithium ion battery and test chemical property.Wherein, first discharge specific capacity, 1C Xun Huans
The specific discharge capacity under capacity retention ratio and 10C after 80 circles refers to table 1.
Table 1
It can be learnt by table 1：Solid electrolyte of the present invention is compared with Li2SnO3In LiCoO2Significantly change in half-cell
It has been apt to cyclical stability and high rate performance.
LiCoO after fast-ionic conductor of the present invention cladding2、LiNi0.6Co0.2Mn0.2O2、
Li1.2Ni0.2Mn0.6O2Discharge capacity remains basically stable with uncoated sample for the first time；
LiCoO after fast-ionic conductor of the present invention cladding2、LiNi0.6Co0.2Mn0.2O2、
Li1.2Ni0.2Mn0.6O2Under 1C after 80 circle of cycle capacity retention ratio be promoted to 85% by 45%, 75%, 65% respectively, 90%,
85%, effectively improve the cyclical stability of above-mentioned positive electrode.
By Li1.6Mg1.6Sn2.8O8LiCoO after cladding2、LiNi0.6Co0.2Mn0.2O2、Li1.2Ni0.2Mn0.6O2In 10C
Under specific discharge capacity be promoted to 153.6 by 37.9,136.3,103.3mAh/g respectively, 171,143.2mAh/g, significantly improve
Specific discharge capacity of the above-mentioned positive electrode under high magnification.
By Li1.4Co1.4Sn2.6O8LiCoO after cladding2、LiNi0.6Co0.2Mn0.2O2、Li1.2Ni0.2Mn0.6O2In 10C
Under specific discharge capacity be promoted to 157.2 by 37.9,136.3,103.3mAh/g respectively, 172.8,140.7mAh/g, significantly carry
High specific discharge capacity of the above-mentioned positive electrode under high magnification.
By Li1.6Zn1.6Sn2.8O8LiCoO after cladding2、LiNi0.6Co0.2Mn0.2O2、Li1.2Ni0.2Mn0.6O2In 10C
Under specific discharge capacity be promoted to 143.7 by 37.9,136.3,103.3mAh/g respectively, 167.4,133.1mAh/g, significantly carry
High specific discharge capacity of the above-mentioned positive electrode under high magnification.
More than content is only citing made for the present invention and explanation, and affiliated those skilled in the art are to being retouched
The specific embodiment stated does various modifications or additions or substitutes in a similar way, without departing from the design of invention
Or surmount scope defined in the claims, it is within the scope of protection of the invention.
Claims (9)
1. a kind of fast-ionic conductor, by LixMySnzO8It represents, the one kind of wherein M in Mg, Co and Zn, 1<x<2.5,1<y<
2.5,2.0<z<3.5.
2. a kind of positive electrode for lithium ion battery coated by fast-ionic conductor according to claim 1, wherein,
The fast-ionic conductor forms homogeneous clad on the surface of the positive electrode for lithium ion battery, based on 100 weights
The positive electrode for lithium ion battery of % is measured, the amount of the new fast-ionic conductor is 0.1 weight % to 10 weights
Measure %.
3. the positive electrode for lithium ion battery of fast-ionic conductor cladding according to claim 1, wherein, the use
LiCoO is selected from the positive electrode of lithium ion battery2；LiNi0.5Mn1.5O4；LiNi0.8Co0.15Al0.05O2；LiNiaCo1-aO2,
In, 0 ＜ a ＜ 1；LiNibCocMn1-b-cO2, wherein, 0 ＜ b ＜, 1,0 ＜ c ＜ 1；And Li2MnO3·LiNidCoeMn1-d-eO2, wherein
0 ＜ d ＜, 1,0 ＜ e ＜ 1.
4. a kind of method for the positive electrode for lithium ion battery for preparing the new fast-ionic conductor cladding, the method
Include the following steps：
(1) stoichiometrically lithium salts, M salt, pink salt are dissolved in deionized water or alcohol, are optionally added into acid, stirred to complete
Dissolving；
(2) aqueous slkali is added dropwise into the solution that step (1) obtains and adjusts pH value to 8.0~10.0, obtains sinking containing hydroxide
The suspension in shallow lake；
(3) positive electrode that lithium battery is used for described in graininess or stratiform is added in the suspension obtained by step (2), stirred
It mixes, then dries；
(4) by the powder mull of gained in step (3), then under conditions of air, calcining heat is at 500~950 DEG C, 3~5
DEG C/min heatings, 2-12h is calcined, the positive electrode for lithium ion battery of fast-ionic conductor cladding can be obtained；
Wherein, gained new fast-ionic conductor coat positive electrode in, based on described in 100 weight % be used for lithium ion
The positive electrode of battery, the amount of the new fast-ionic conductor is 0.1 weight % to 10 weight %,
The M salt is selected from magnesium salts, cobalt salt and zinc salt.
5. according to the method described in claim 4, wherein,
The lithium salts is selected from lithium carbonate, lithium nitrate, lithium hydroxide or lithium acetate；
The magnesium salts is selected from magnesium nitrate, magnesium chloride, magnesium acetate, magnesium citrate or magnesium ethylate；
The cobalt salt is selected from cobalt acetate, cobalt nitrate or cobaltous sulfate；
The zinc salt is selected from zinc acetate, zinc nitrate, zinc chloride or zinc sulfate；
The pink salt is selected from stannic chloride, stannous chloride, stannous sulfate, nitric acid tin, nitric acid stannous or tin acetate.
6. according to the method described in claim 4, wherein, the positive electrode is usually graininess or stratified material, for
In the case of granular, granularity D50For 2 to 20 microns.
7. a kind of anode for lithium ion battery, it includes the use of the fast-ionic conductor cladding according to Claims 2 or 3
In the positive electrode of lithium ion battery.
8. a kind of purposes of fast-ionic conductor according to claim 1 as the electrolyte of lithium ion battery.
9. a kind of lithium ion battery, including anode according to claim 7 and/or according to claim 1 fast
Ion conductor is as electrolyte.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101969110A (en) * | 2010-08-31 | 2011-02-09 | 天津巴莫科技股份有限公司 | Fast ion conductor modified lithium ion battery cathode material lithium cobalt oxide with fast ion conductor and preparation method |
| CN102522547A (en) * | 2011-12-28 | 2012-06-27 | 彩虹集团公司 | Preparation method for lithium ion fast conductor modified lithium iron phosphate material |
| CN104183849A (en) * | 2014-08-12 | 2014-12-03 | 江苏大学 | Preparation method of solid solution positive material covering surface of fast ionic conductor |
-
2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101969110A (en) * | 2010-08-31 | 2011-02-09 | 天津巴莫科技股份有限公司 | Fast ion conductor modified lithium ion battery cathode material lithium cobalt oxide with fast ion conductor and preparation method |
| CN102522547A (en) * | 2011-12-28 | 2012-06-27 | 彩虹集团公司 | Preparation method for lithium ion fast conductor modified lithium iron phosphate material |
| CN104183849A (en) * | 2014-08-12 | 2014-12-03 | 江苏大学 | Preparation method of solid solution positive material covering surface of fast ionic conductor |
Non-Patent Citations (2)
| Title |
|---|
| J. CHOISNET等: "UNE NOUVELLE STRUCTURE HEXAGONALE COMPACTE ORDONNEE :LES OXYDES ︳Sn-X3︳octa ︳M-Li︳tetraO8 , avec X = Sn(Ti)+ M + Li et M = Zn, Mg.", 《MATERIALS RESEARCH BULLTIN》 * |
| T. TRENDAFILOVA 等，: "《Cation distribution in Li2M(II)Sn3O8,M(II) = Mg, Co, Fe》", 《EUROPEAN POWDER DIFFRACTION CONFERENCE》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109904424A (en) * | 2019-02-28 | 2019-06-18 | 河南大学 | The method of one-step method surface cladding and the double modification LNMO positive electrodes of grade doping integration |
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