CN110085827A - A kind of lithium-rich manganese-based anode material and its preparation method and application - Google Patents
A kind of lithium-rich manganese-based anode material and its preparation method and application Download PDFInfo
- Publication number
- CN110085827A CN110085827A CN201910329781.1A CN201910329781A CN110085827A CN 110085827 A CN110085827 A CN 110085827A CN 201910329781 A CN201910329781 A CN 201910329781A CN 110085827 A CN110085827 A CN 110085827A
- Authority
- CN
- China
- Prior art keywords
- lithium
- anode material
- based anode
- rich manganese
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of lithium-rich manganese-based anode material and its preparation method and application, chemical formula xLi2MnO3·(1‑x)LiMSnyCezO2, in which: at least two in M Ni, Co and Mn, 0.2≤x≤0.8,0.005≤y≤0.02,0.01≤z≤0.05.The present invention passes through two kinds of elements of doped tin cerium, the crystal structure of lithium-rich manganese-based anode material obtained is more stable, coulombic efficiency and high rate performance are improved lithium-rich manganese-based anode material after cerium tin codope for the first time, and cyclical stability is significantly improved, especially, the decaying of voltage has obtained apparent inhibition in cyclic process；In addition, the preparation method simple process, preparing presoma using hydroxyl coprecipitation reaction, combined coefficient is high, is suitble to large-scale production.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries technical fields, in particular to a kind of lithium-rich manganese-based anode material
Material and its preparation method and application.
Background technique
With the continuous progress of science and technology with the continuous growth of people's demand, development manufacture high-performance, frivolous, cost drop increasingly
Low lithium ion battery is still the research and development focus of people.Low energy consumption because it has for lithium ion battery, and specific capacity and specific energy are high, work
Make voltage height, environmental-friendly, good cycle, the remarkable advantages such as service life length are widely used in laptop, mobile electricity
Words, the portable electronic devices such as camera.Wherein, positive electrode seriously restricts lithium ion secondary battery power density, energy
Density further increases, so it is particularly important to develop high-performance lithium ion positive electrode of new generation.Lithium-rich manganese-based anode material
After report take the lead in from Numata in 1997 etc., extensive research is just obtained, the specific capacity of lithium-rich manganese base material can achieve
300mAh/g, capacity are lifted beyond 50% compared with other positive electrodes, and voltage is up to 4.8V, much higher than ternary material and other anodes
Material, while lithium-rich manganese base material uses more lower-cost Mn element, so that the cost of lithium-rich manganese base material
A kind of next-generation positive electrode with great potential far below ternary material and other positive electrodes, can help lithium from
Sub- battery initiates to challenge towards specific energy 300Wh/kg.
However, there are still some problems that its large-scale commercial application is made to be restricted for lithium-rich manganese base material itself, such as
Biggish irreversible capacity loss, poor cyclical stability and multiplying power are put in the low capacity of positive electrode, cyclic process for the first time
Electrical property, voltage attenuation are serious etc., become the main bottleneck of such material in practical applications.Cause the main original of these problems
Because being attributed in system, there are a large amount of Li2MnO3, it is unfavorable for the conduction of electronics and forms the induction of a large amount of superlattice structures stacking
Fault and lithium nickel mix, and limit the migration of lithium ion, and material capacity under high magnification is caused to be decreased obviously and cycle performance
It is gradually reduced.Secondly, the performance of the material high capacity has benefited from the common abjection of oxygen and lithium at 4.5V, however the oxygen deviate from
Cannot be reduced in discharge process afterwards, so as to cause the biggish irreversible capacity loss of first circle and transition metal ions to
The migration of internal layer is reset, and is caused phase transition in cyclic process, is led to the decaying of voltage and capacity.In order to further increase its electricity
Chemical property, can meet the use standard of power lithium-ion battery material, and the emphasis studied at present is exactly to be to improve it
Cyclic process in voltage attenuation.Therefore the research that various doping or coating modification lithium-rich anode material have been goed deep into,
To improve interface stability, improves oxygen and be lost, reduce the voltage attenuation in cyclic process.
Application publication number is that the Chinese invention patent application of CN107069026A discloses a kind of effectively inhibition cyclic process
Stratiform richness lithium manganese oxide anode material of middle capacity/voltage attenuation and its preparation method and application, this method include following step
It is rapid: during lithium ion battery stratiform richness lithium manganese oxide anode material precursor preparation, LiNiO is added2Raw material before
Body is driven, then high-temperature heat treatment obtains stratiform richness lithium manganese oxide anode material.LiNiO is used in method2For modified material, benefit
With preparation methods such as spray pyrolysis, collosol and gel, co-precipitation, wherein using in Co-precipitation, by Li, Ni, Co,
The acetate of Mn is added in a certain amount of deionized water, and then acetate lithium and acetate nickel are added in reaction solution, is used
Ammonium hydroxide adjusts pH, dry then by filtering, and obtains LiNiO after heat treatment2The rich lithium manganese oxide anode material of doping.It should
Cycle performance test is to carry out under 20mA/g current density, but its current density is smaller in method, is much smaller than practical application
Current density, it is difficult to be widely applied in practice.
Summary of the invention
In consideration of it, the invention proposes a kind of lithium-rich manganese-based anode materials and its preparation method and application, it is intended to solve existing
There is the serious problem that decays in lithium-rich manganese-based anode material cyclic process.
First aspect present invention proposes a kind of lithium-rich manganese-based anode material, chemical formula xLi2MnO3·(1-x)
LiMSnyCezO2, in which: at least two in M Ni, Co and Mn, 0.2≤x≤0.8,0.005≤y≤0.02,0.01≤z≤
0.05。
Second aspect of the present invention proposes a kind of preparation method of lithium-rich manganese-based anode material, comprising the following steps:
Step 1, according to the stoichiometric ratio of chemical formula, prepare Sn salt, Ce salt, manganese salt and M salt aqueous solution, and mix equal
It is even, obtain mixed solution；Wherein, at least two in M element Ni, Co and Mn；
Step 2, reactor is added in the mixed solution and strong base solution simultaneously, is carried out under the first preset temperature coprecipitated
It forms sediment and reacts, and add appropriate complexing agent, after reacting a period of time, by washing, filtering and drying, obtain transition metallic hydrogen oxygen root
Presoma；
Step 3, the presoma and lithium salts are sufficiently mixed uniformly with the ratio between the amount of preset substance, in the second default temperature
It degree lower pretreatment a period of time, is then warming up under third preset temperature and calcines a period of time, be cooled to room temperature, it is total to obtain tin cerium
The lithium-rich manganese-based anode material of doping.
Further, in the preparation method of above-mentioned lithium-rich manganese-based anode material, the manganese salt is Mn (NO3)2And/or Mn
(CH3COO)2；The M salt is the nitrate and/or sulfate of nickel, cobalt or manganese.
Further, in the preparation method of above-mentioned lithium-rich manganese-based anode material, the Sn salt is stannic chloride, nitric acid tin and sulphur
At least one of sour tin；The Ce salt is at least one of cerium chloride, cerous sulfate and cerous nitrate.
Further, in the preparation method of above-mentioned lithium-rich manganese-based anode material, the Sn ion and the Ce ion it is total
The ratio between the amount of substance and the amount of total material of the manganese ion and the M ion are 1:(15-25).
Further, in the preparation method of above-mentioned lithium-rich manganese-based anode material, the object of the Sn ion and the Ce ion
The amount ratio of matter is 0.1~0.4.
Further, in the preparation method of above-mentioned lithium-rich manganese-based anode material, the amount of the substance of M ion is dense in the M salt
Degree is 1.5-2.5mol/L.
Further, in the preparation method of above-mentioned lithium-rich manganese-based anode material, the highly basic is sodium hydroxide, potassium hydroxide
Or both mixture；The complexing agent is ammonium hydroxide；The lithium salts is one of lithium carbonate, lithium hydroxide and lithium oxalate or more
Kind.
Further, in the preparation method of above-mentioned lithium-rich manganese-based anode material, in the step 2, contain Sn and Ce element
Metal salt solution and the pH value of solution is 11-12 when the co-precipitation of M salting liquid.
Further, in the preparation method of above-mentioned lithium-rich manganese-based anode material, in the step 3, the presoma and institute
Stating the ratio between amount of substance of elemental lithium in lithium salts is 1:1.4~1.6.
Further, in the preparation method of above-mentioned lithium-rich manganese-based anode material, first preset temperature is 40-80 DEG C；
Second preset temperature is 400-500 DEG C；The third preset temperature is 600-1000 DEG C.
The preparation method for the lithium-rich manganese-based anode material that second aspect of the present invention provides, by two kinds of elements of doped tin cerium,
Be able to suppress the migration and dissolution of transition metal, fixed Lattice Oxygen, make the crystal structure of lithium-rich manganese-based anode material obtained compared with
Stablize, coulombic efficiency and high rate performance are improved the lithium-rich manganese-based anode material after cerium tin codope for the first time, and are circulated throughout
The stability of capacity is significantly improved in journey, and especially, the decaying of voltage has obtained apparent inhibition in cyclic process；This
Outside, the preparation method simple process, prepare presoma using hydroxyl coprecipitation reaction, combined coefficient is high, is suitble to scale metaplasia
It produces.
Third aspect present invention provides a kind of lithium ion cell positive, uses above-mentioned lithium-rich manganese-based anode material system
At.
Since above-mentioned lithium-rich manganese-based anode material has excellent high rate performance and cycle performance, it is made of it
Lithium ion cell positive also have the advantages that this.
Fourth aspect present invention additionally provides a kind of lithium ion battery, uses above-mentioned anode, can be with deintercalate lithium ions
Cathode and between the cathode and anode electrolyte composition.
Detailed description of the invention
The X-ray for the lithium-rich manganese-based anode material that Fig. 1 is 1-4 of the embodiment of the present invention and comparative example 1 is prepared respectively is spread out
Penetrate (XRD) figure；
The first charge-discharge for the lithium-rich manganese-based anode material that Fig. 2 is 1-4 of the embodiment of the present invention and comparative example 1 is prepared respectively is bent
Line comparison diagram；
Fig. 3 be the cerium tin codope that 1-4 of the embodiment of the present invention and comparative example 1 are prepared respectively lithium-rich manganese-based anode material and
The high rate performance curve of comparative example original material；
Fig. 4 a is the differential capacity curve of lithium-rich manganese-based anode material prepared by comparative example 1；
Fig. 4 b is the differential capacity curve of the lithium-rich manganese-based anode material of cerium tin codope prepared by the embodiment of the present invention 1；
Fig. 4 c is the differential capacity curve of the lithium-rich manganese-based anode material of cerium tin codope prepared by the embodiment of the present invention 2；
Fig. 4 d is the differential capacity curve of the lithium-rich manganese-based anode material of cerium tin codope prepared by the embodiment of the present invention 3；
Fig. 4 e is the differential capacity curve of the lithium-rich manganese-based anode material of cerium tin codope prepared by the embodiment of the present invention 4；
Fig. 5 is the voltage attenuation curve pair for the lithium-rich manganese-based anode material that the embodiment of the present invention 1 and comparative example 1 are prepared respectively
Than figure.
Specific embodiment
The following is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principle of the present invention, some improvements and modifications can also be made, these improvement and modification are also considered as
Protection scope of the present invention.
The present invention provides a kind of lithium-rich manganese-based anode material, chemical formula xLi2MnO3·(1-x)LiMSnyCezO2,
Wherein: at least two in M Ni, Co and Mn, 0.2≤x≤0.8,0.005≤y≤0.02,0.01≤z≤0.05.Wherein,
Preferably, 0.3≤x≤0.5,0.008≤y≤0.01,0.02≤z≤0.03.Due to original material xLi2MnO3·(1-x)
LiMO2Li can be deviate from during initial charge2O and O2, to generate the vacancy Li and Lacking oxygen, lead to the migration of transition metal
And dissolution, and the doping of Ce and Sn element can occupy Li2O and O2Deviate from the vacancy generated, the stabilization of lattice is kept, to inhibit
The migration and dissolution of transition metal are able to maintain the good crystal structure of material, to improve original material xLi2MnO3·(1-
x)LiMO2Chemical property.
The invention also provides the preparation methods of lithium-rich manganese-based anode material, comprising the following steps:
Step 1, according to stoichiometric ratio, prepare Sn salt, Ce salt, manganese salt and M salt aqueous solution, and be uniformly mixed, obtain
Mixed solution；Wherein, at least two in M element Ni, Co and Mn.
Specifically, manganese salt can be Mn (NO3)2And/or Mn (CH3COO)2；Due to transition metal M element be Ni, Co and
At least two in Mn, therefore, the M salt can be the nitrate and/or sulfate of nickel, cobalt or manganese.Such as when M salt is nickel salt
When, it can be at least one of the nitrate of nickel and sulfate；When M salt be cobalt salt when, can for cobalt nitrate and
At least one of sulfate；It can be at least one of the nitrate of manganese and sulfate when M salt is manganese salt；When M salt
It can be the combination of any one or more in nickel salt and manganese salt when for the mixture of manganese salt and nickel salt.
Sn salt can be at least one of stannic chloride, nitric acid tin and STANNOUS SULPHATE CRYSTALLINE；The Ce salt can be cerium chloride, sulfuric acid
At least one of cerium and cerous nitrate.
In the step, the amount of the total material of the Sn ion and the Ce ion and the manganese ion and the M ion
The ratio between amount of total material is 1:(15-25)；Preferably 1:20.Wherein, the mass ratio of the material value of Sn ion and the Ce ion is
0.1~0.4, such as the ratio between amount of substance of Sn ion and the Ce ion can be 0.1:0.9,0.2:0.8,0.3:0.7 etc..
More specifically, the substance withdrawl syndrome of M ion is 1.5-2.5mol/L in M salt.It should be noted that the object of ion
The amount concentration of matter refers to the sum of the substance withdrawl syndrome of all transition metal ions in M salt.
Step 2, reactor is added in the mixed solution and strong base solution simultaneously, is carried out under the first preset temperature coprecipitated
It forms sediment and reacts, and add appropriate complexing agent, after reacting a period of time, by washing, filtering and drying, obtain transition metallic hydrogen oxygen root
Presoma.
Specifically, highly basic can be the mixture of sodium hydroxide, potassium hydroxide or both；Complexing agent can be ammonium hydroxide.
Preferably, the concentration of highly basic can be 3-5mol/L.Twice of the concentration of highly basic substantially M salt intermediate ion concentration, can make
The volume being added dropwise both in reaction process is the same, convenient for the control to coprecipitation reaction.The addition of highly basic is conducive to hydroxide
The generation of object precipitating, meanwhile, complexing agent is added, it can be with the pH value of buffer solution, so that precipitating forming core is rapider, so that sediment
Partial size it is also more uniform.
When it is implemented, first preset temperature can be 40-80 DEG C, preferably 50-70 DEG C, more preferably 60 DEG C.
In the step, the pH value of the metal salt solution containing Sn and Ce element and solution when the co-precipitation of M salting liquid is 11-
12, wherein pH value can be adjusted jointly by highly basic and complexing agent ammonium hydroxide, to promote the coprecipitation reaction of each metal ion.
The molecular formula of presoma obtained can be Ni0.13Co0.13Mn0.54SnyCez(OH)1.6+σ, wherein 0.02≤σ≤0.08.Step
3, the presoma and lithium salts are sufficiently mixed uniformly with the ratio between the amount of preset substance, pre-process one under the second preset temperature
Then the section time is warming up under third preset temperature and calcines a period of time, is cooled to room temperature, obtains the rich lithium manganese of tin cerium codope
Base anode material.
Specifically, lithium salts can be one of lithium carbonate, lithium hydroxide and lithium oxalate or a variety of.It can be by mixture
It is placed in Muffle furnace and carries out pretreatment and calcination processing.
When it is implemented, the ratio between the amount of substance of elemental lithium in presoma and the lithium salts can be 1:1.4~1.6,
Preferably 1:1.5.Second preset temperature can be 400-500 DEG C, preferably 450 DEG C；Pretreatment time can be 4-6h, preferably
For 5h；Third preset temperature is 600-1000 DEG C, preferably 750-900 DEG C；Calcination time can be 12-18h.
The advantage of kind lithium-rich manganese-based anode material provided for the present invention will be described in detail embodiment and preparation method thereof, under
Using comparative example and specific embodiment, the present invention will be described in face.
Embodiment 1
(1) by the mixed liquor and substance of pink salt and cerium salt that the ratio between amount of substance of tin ion and cerium ion is 0.1:0.9
Amount concentration be 2mol/L nickel, cobalt, manganese mixing salt solution be sufficiently mixed uniformly；
(2) reactor is added in the strong base solution that above-mentioned solution and substance withdrawl syndrome are 4mol/L simultaneously, at 60 DEG C
Under the conditions of carry out coprecipitation reaction, during which add suitable ammonium hydroxide as complexing agent.After reaction, transition metallic hydrogen oxygen is obtained
Root presoma precipitating, then by being filtered by vacuum, washing, filtering, being dried to obtain precursor powder material；
(3) transition metal hydroxyl precursor powder and lithium salts is sufficiently mixed for the ratio of 1.5:1 with the ratio between amount of substance
It closes uniformly, is placed in Muffle furnace at 450 DEG C and pre-processes 5h, be then warming up at 900 DEG C and calcine 12h, be cooled to room temperature, obtain
The lithium-rich manganese-based anode material of tin cerium codope, chemical formula 0.5Li2MnO3·0.5LiNi1/3Sn0.005Ce0.045Co1/ 3Mn1/3O2。
Embodiment 2
(1) by the mixed liquor and substance of pink salt and cerium salt that the ratio between amount of substance of tin ion and cerium ion is 0.3:0.7
Amount concentration be 2mol/L nickel, cobalt, manganese mixing salt solution be sufficiently mixed uniformly；
(2) reactor is added in the strong base solution that above-mentioned solution and substance withdrawl syndrome are 4mol/L simultaneously, at 60 DEG C
Under the conditions of carry out coprecipitation reaction, during which add suitable ammonium hydroxide as complexing agent.After reaction, transition metallic hydrogen oxygen is obtained
Root presoma precipitating, then by being filtered by vacuum, washing, filtering, being dried to obtain precursor powder material；
(3) transition metal hydroxyl precursor powder and lithium salts is sufficiently mixed for the ratio of 1.5:1 with the ratio between amount of substance
It closes uniformly, is placed in Muffle furnace at 450 DEG C and pre-processes 5h, be then warming up at 900 DEG C and calcine 12h, be cooled to room temperature, obtain
The lithium-rich manganese-based anode material of tin cerium codope, chemical formula 0.5Li2MnO3·0.5LiNi1/3Sn0.01Ce0.023Co1/3Mn1/ 3O2。
Embodiment 3
(1) by the mixed liquor and substance of pink salt and cerium salt that the ratio between amount of substance of tin ion and cerium ion is 0.2:0.8
Amount concentration be 2mol/L nickel, cobalt, manganese mixing salt solution be sufficiently mixed uniformly；
(2) reactor is added in the strong base solution that above-mentioned solution and substance withdrawl syndrome are 4mol/L simultaneously, at 70 DEG C
Under the conditions of carry out coprecipitation reaction, during which add suitable ammonium hydroxide as complexing agent.After reaction, transition metallic hydrogen oxygen is obtained
Root presoma precipitating, then by being filtered by vacuum, washing, filtering, being dried to obtain precursor powder material；
(3) transition metal hydroxyl precursor powder and lithium salts is sufficiently mixed for the ratio of 1.5:1 with the ratio between amount of substance
It closes uniformly, is placed in Muffle furnace at 450 DEG C and pre-processes 5h, be then warming up at 900 DEG C and calcine 18h, be cooled to room temperature, obtain
The lithium-rich manganese-based anode material of tin cerium codope, chemical formula 0.5Li2MnO3·0.5LiNi1/3Sn0.008Ce0.032Co1/ 3Mn1/3O2。
Embodiment 4
(1) by the mixed liquor and substance of pink salt and cerium salt that the ratio between amount of substance of tin ion and cerium ion is 0.1:0.9
Amount concentration be 1.5mol/L nickel, cobalt, manganese mixing salt solution be sufficiently mixed uniformly；
(2) reactor is added in the strong base solution that above-mentioned solution and substance withdrawl syndrome are 3mol/L simultaneously, at 60 DEG C
Under the conditions of carry out coprecipitation reaction, during which add suitable ammonium hydroxide as complexing agent.After reaction, transition metallic hydrogen oxygen is obtained
Root presoma precipitating, then by being filtered by vacuum, washing, filtering, being dried to obtain precursor powder material；
(3) transition metal hydroxyl precursor powder and lithium salts is sufficiently mixed for the ratio of 1.5:1 with the ratio between amount of substance
It closes uniformly, is placed in Muffle furnace at 500 DEG C and pre-processes 5h, be then warming up at 900 DEG C and calcine 15h, be cooled to room temperature, obtain
The lithium-rich manganese-based anode material of tin cerium codope, chemical formula 0.5Li2MnO3·0.5LiNi1/3Sn0.005Ce0.045Co1/ 3Mn1/3O2。
Comparative example 1
Rapid coprecipitation method is used to prepare chemical formula as 0.5Li2MnO3·0.5LiNi1/3Co1/3Mn1/3O2It is lithium-rich manganese-based
Positive electrode；Specific preparation process is as follows for it:
(1) nickel, cobalt, manganese salt solution that amount concentration of the preparation containing transition metal material is 2mol/L, are uniformly mixed；
(2) reactor is added in the strong base solution that above-mentioned solution and substance withdrawl syndrome are 4mol/L simultaneously, at 60 DEG C
Under the conditions of carry out coprecipitation reaction, during which add suitable ammonium hydroxide as complexing agent.After reaction, transition metallic hydrogen oxygen is obtained
Root presoma precipitating, then by being filtered by vacuum, washing, filtering, being dried to obtain precursor powder material；
(3) lithium salts of powder transition metal hydroxyl presoma and the amount of certain substance is sufficiently mixed uniformly, is placed in horse
5h is not pre-processed in furnace at 450 DEG C, is then warming up at 900 DEG C and calcines 12h, be cooled to room temperature, obtain lithium-rich manganese-based anode
Material.
Experimental example
In order to verify the structure of lithium-rich manganese-based anode material prepared by the embodiment of the present invention, to embodiment 1-2 and comparative example 1
In lithium-rich manganese-based anode material carried out XRD test respectively.As a result as shown in Figure 1:
As seen from Figure 1: in embodiment 1-2 and the lithium-rich manganese-based anode material of tin cerium codope obtained by comparative example 1
Material is layer structure and structural integrity, in addition, occur new diffraction maximum in the XRD diffracting spectrum of Examples 1 and 2, it is corresponding
The characteristic peak of ceria, and occur without other impurity peaks, show that a small amount of tin cerium enters in material lattice, it is most of
Cerium ion may be embedded into lithium layer.
It, will be in embodiment 1-4 in order to verify the chemical property of lithium-rich manganese-based anode material prepared by the embodiment of the present invention
Lithium-rich manganese-based anode material prepared by the lithium-rich manganese-based anode material of the tin cerium codope of preparation and comparative example 1, respectively with Super
P (conductive black) and PVDF (Kynoar) 75:15:10 in mass ratio carries out slurrying and is coated with, and being then cut into diameter is
12mm pole piece, using metal lithium sheet as cathode, electrolyte uses the high pressure resistant electrolyte of Shenzhen Xinzhoubang Technology Co., Ltd,
It is assembled into half-cell in argon gas glove box and carries out electrochemical property test, all electrochemical property tests are in room temperature below
Lower progress.
It as shown in Figure 2, is 12.5mA/g, voltage range 2.0- in the current density of the first charge-discharge curve of battery
Under conditions of 4.8V, the discharge capacity for the first time of the lithium-rich manganese-based anode material of the tin cerium codope of embodiment 1-4 preparation is compared
Ratio 1 is high, wherein embodiment 3, the discharge capacity of embodiment 4 respectively reach 296.3mAh/g, 300mAh/g, are both significantly higher than
282.0mAh/g in comparative example is much higher by comparative example 1 in addition, the first charge-discharge efficiency of embodiment 3 reaches 83.78%
77.63%, reduce irreversible capacity loss for the first time.As shown in figure 3, first using lesser before high rate performance test
The current density of 12.5mA/g is activated twice, then use in same voltage range respectively with 12.5mA/g, 25mA/g,
50mA/g, 125mA/g, 250mA/g (1C), 500mA/g, 1250mA/g current density under discharge, the density of charging current
It is 25mA/g, as seen from Figure 3, the electric discharge ratio of the lithium-rich manganese-based anode material of the tin cerium codope of embodiment 1-4 preparation
Capacity is above the specific discharge capacity of comparative example 1, and especially when multiplying power is 5C, the specific discharge capacity of embodiment 3 reaches
176.4mAh/g, much higher than the 160.4mAh/g of comparative example 1, meanwhile, the high rate performance of embodiment 1-4 relative to comparative example 1 and
Speech also has significantly improved；The peak shift of Differential Capacity curve from Fig. 4 a to 4e is, it is apparent that the embodiment of the present invention 1
Voltage attenuation of the lithium-rich manganese-based anode material of middle preparation in cyclic process has obtained apparent inhibition；As seen from Figure 5,
The battery assembled by the lithium-rich manganese-based anode material of the tin cerium codope in embodiment 1 is after 100 circulations, voltage attenuation
0.3527V, and the 0.5246V that decayed under similarity condition in comparative example 1, it can be seen that the richness of tin cerium dopping prepared by embodiment 1
Lithium manganese-based anode material can effectively inhibit the attenuation degree of voltage in cyclic process.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (13)
1. a kind of lithium-rich manganese-based anode material, which is characterized in that the chemical formula of the lithium-rich manganese-based anode material is xLi2MnO3·
(1-x)LiMSnyCezO2, in which: at least two in M Ni, Co and Mn, 0.2≤x≤0.8,0.005≤y≤0.02,0.01
≤z≤0.05。
2. a kind of preparation method of lithium-rich manganese-based anode material as described in claim 1, which is characterized in that including following step
It is rapid:
Step 1, according to stoichiometric ratio, prepare Sn salt, Ce salt, manganese salt and M salt aqueous solution, and be uniformly mixed, mixed
Solution；Wherein, at least two in M element Ni, Co and Mn；
Step 2, reactor is added in the mixed solution and strong base solution simultaneously, carries out being co-precipitated under the first preset temperature anti-
It answers, and adds appropriate complexing agent, after reacting a period of time, by washing, filtering and drying, obtain transition metallic hydrogen oxygen root forerunner
Body；
Step 3, the presoma and lithium salts are sufficiently mixed uniformly, under the second preset temperature with the ratio between the amount of preset substance
It pretreatment a period of time, is then warming up under third preset temperature and calcines a period of time, be cooled to room temperature, obtain tin cerium codope
Lithium-rich manganese-based anode material.
3. the preparation method of lithium-rich manganese-based anode material according to claim 2, which is characterized in that the manganese salt is Mn
(NO3)2And/or Mn (CH3COO)2；The M salt is the nitrate and/or sulfate of nickel, cobalt or manganese.
4. the preparation method of lithium-rich manganese-based anode material according to claim 2, which is characterized in that the Sn salt is chlorination
At least one of tin, nitric acid tin and STANNOUS SULPHATE CRYSTALLINE；The Ce salt is at least one of cerium chloride, cerous sulfate and cerous nitrate.
5. the preparation method of lithium-rich manganese-based anode material according to claim 2, which is characterized in that the Sn ion and institute
The ratio between the amount of the total material of Ce ion and the amount of total material of the manganese ion and the M ion are stated as 1:(15-25).
6. the preparation method of lithium-rich manganese-based anode material according to claim 2, which is characterized in that the Sn ion and institute
The mass ratio of the material value for stating Ce ion is 0.1~0.4.
7. the preparation method of lithium-rich manganese-based anode material according to claim 2, which is characterized in that M ion in the M salt
Substance withdrawl syndrome be 1.5-2.5mol/L.
8. the preparation method of lithium-rich manganese-based anode material according to claim 2, which is characterized in that the highly basic is hydrogen-oxygen
Change the mixture of sodium, potassium hydroxide or both；The complexing agent is ammonium hydroxide；The lithium salts is lithium carbonate, lithium hydroxide and oxalic acid
One of lithium is a variety of.
9. the preparation method of lithium-rich manganese-based anode material according to claim 2, which is characterized in that in the step 2, contain
The pH value of solution is 11-12 when having metal salt solution and the co-precipitation of M salting liquid of Sn and Ce element.
10. the preparation method of lithium-rich manganese-based anode material according to claim 2, which is characterized in that in the step 3,
The ratio between amount of substance of elemental lithium in the presoma and the lithium salts is 1:1.4~1.6.
11. the preparation method of lithium-rich manganese-based anode material according to claim 2, which is characterized in that described first is default
Temperature is 40-80 DEG C；Second preset temperature is 400-500 DEG C；The third preset temperature is 600-1000 DEG C.
12. a kind of lithium ion cell positive, which is characterized in that use lithium-rich manganese-based anode material system as described in claim 1
At.
13. a kind of lithium ion battery, which is characterized in that use as claimed in claim 13 anode, can be with deintercalate lithium ions
Cathode and the electrolyte composition between the cathode and anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910329781.1A CN110085827A (en) | 2019-04-23 | 2019-04-23 | A kind of lithium-rich manganese-based anode material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910329781.1A CN110085827A (en) | 2019-04-23 | 2019-04-23 | A kind of lithium-rich manganese-based anode material and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110085827A true CN110085827A (en) | 2019-08-02 |
Family
ID=67416170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910329781.1A Pending CN110085827A (en) | 2019-04-23 | 2019-04-23 | A kind of lithium-rich manganese-based anode material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110085827A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111509224A (en) * | 2020-04-17 | 2020-08-07 | 中南大学 | Linked modified lithium-rich manganese-based cathode material and preparation method thereof |
| CN115650305A (en) * | 2022-10-17 | 2023-01-31 | 昆明理工大学 | Preparation method of cerium-doped lithium-rich manganese-based positive electrode material |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011162195A1 (en) * | 2010-06-21 | 2011-12-29 | 日本碍子株式会社 | Method for producing spinel lithium manganese oxide |
| CN105355907A (en) * | 2015-12-10 | 2016-02-24 | 哈尔滨工业大学 | Lithium metallic oxide precursor material with annual ring type structure, anode material prepared by lithium metallic oxide precursor material, and preparation method and application |
| CN105552327A (en) * | 2015-12-18 | 2016-05-04 | 哈尔滨工业大学 | Lithium metal oxide composite positive electrode material with multilayer structure, precursor material for constituting same, and preparation method and application for precursor material |
| EP3032618A2 (en) * | 2014-12-09 | 2016-06-15 | Samsung SDI Co., Ltd. | Positive active material for rechargeable lithium battery and rechargeable lithium battery |
| CN106328908A (en) * | 2016-11-16 | 2017-01-11 | 吉林化工学院 | Lithium-rich anode material for lithium ion battery and preparation method thereof |
| CN108091843A (en) * | 2017-12-11 | 2018-05-29 | 广东工业大学 | A kind of lithium-rich manganese-based composite positive pole of nucleocapsid and preparation method thereof |
| CN108172808A (en) * | 2018-01-16 | 2018-06-15 | 北京科技大学 | A kind of method of modifying of cerium tin composite oxides cladding lithium-rich manganese-based anode material |
| CN108598463A (en) * | 2018-02-28 | 2018-09-28 | 中国电力科学研究院有限公司 | A kind of preparation method of nano-sheet lithium-rich manganese-based anode material |
| CN109336193A (en) * | 2018-10-21 | 2019-02-15 | 圣戈莱（北京）科技有限公司 | Multielement original position codope ternary material precursor and its preparation method and application |
| CN109455772A (en) * | 2017-12-28 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of preparation method of the lithium ion battery presoma of modification, positive electrode and the presoma and positive electrode |
-
2019
- 2019-04-23 CN CN201910329781.1A patent/CN110085827A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011162195A1 (en) * | 2010-06-21 | 2011-12-29 | 日本碍子株式会社 | Method for producing spinel lithium manganese oxide |
| EP3032618A2 (en) * | 2014-12-09 | 2016-06-15 | Samsung SDI Co., Ltd. | Positive active material for rechargeable lithium battery and rechargeable lithium battery |
| CN105702952A (en) * | 2014-12-09 | 2016-06-22 | 三星Sdi株式会社 | Positive active material for rechargeable lithium battery and rechargeable lithium battery |
| CN105355907A (en) * | 2015-12-10 | 2016-02-24 | 哈尔滨工业大学 | Lithium metallic oxide precursor material with annual ring type structure, anode material prepared by lithium metallic oxide precursor material, and preparation method and application |
| CN105552327A (en) * | 2015-12-18 | 2016-05-04 | 哈尔滨工业大学 | Lithium metal oxide composite positive electrode material with multilayer structure, precursor material for constituting same, and preparation method and application for precursor material |
| CN106328908A (en) * | 2016-11-16 | 2017-01-11 | 吉林化工学院 | Lithium-rich anode material for lithium ion battery and preparation method thereof |
| CN108091843A (en) * | 2017-12-11 | 2018-05-29 | 广东工业大学 | A kind of lithium-rich manganese-based composite positive pole of nucleocapsid and preparation method thereof |
| CN109455772A (en) * | 2017-12-28 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of preparation method of the lithium ion battery presoma of modification, positive electrode and the presoma and positive electrode |
| CN108172808A (en) * | 2018-01-16 | 2018-06-15 | 北京科技大学 | A kind of method of modifying of cerium tin composite oxides cladding lithium-rich manganese-based anode material |
| CN108598463A (en) * | 2018-02-28 | 2018-09-28 | 中国电力科学研究院有限公司 | A kind of preparation method of nano-sheet lithium-rich manganese-based anode material |
| CN109336193A (en) * | 2018-10-21 | 2019-02-15 | 圣戈莱（北京）科技有限公司 | Multielement original position codope ternary material precursor and its preparation method and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111509224A (en) * | 2020-04-17 | 2020-08-07 | 中南大学 | Linked modified lithium-rich manganese-based cathode material and preparation method thereof |
| CN111509224B (en) * | 2020-04-17 | 2021-07-23 | 中南大学 | Linked modified lithium-rich manganese-based cathode material and preparation method thereof |
| CN115650305A (en) * | 2022-10-17 | 2023-01-31 | 昆明理工大学 | Preparation method of cerium-doped lithium-rich manganese-based positive electrode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103855384B (en) | A kind of ternary cathode material of lithium ion battery of rare-earth-doped modification and preparation method thereof | |
| CN103794752A (en) | High voltage nickel lithium manganate cathode materials with core-shell structure and preparation method thereof | |
| CN114005978B (en) | Cobalt-free cathode material and preparation method and application thereof | |
| CN107565122A (en) | A kind of preparation method of doping type nickel-cobalt lithium manganate cathode material | |
| CN110429268A (en) | A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof | |
| CN102709525B (en) | Metal oxide coated lithium nickel manganese oxide material, preparation method of metal oxide coated lithium nickel manganese oxide material and lithium ion battery | |
| CN106784726B (en) | Lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material and preparation method thereof | |
| CN107204423A (en) | A kind of preparation method and applications of high magnification tertiary cathode material | |
| CN104795555A (en) | Aqueous-solution sodium-ion battery and cathode material, preparation method and application thereof | |
| CN114520318B (en) | High-nickel cobalt-free nickel tungsten lithium manganate positive electrode material for power battery and preparation method | |
| CN109301207A (en) | A kind of surface layer doping Ce3+And surface layer coats CeO2NCM tertiary cathode material and preparation method thereof | |
| CN103078099A (en) | Anode material for lithium ion cell and preparation method thereof | |
| CN104979549A (en) | Sheet lithium-enriched manganese-based anode material for lithium-ion battery as well as preparation method and application of sheet lithium-enriched manganese-based anode material | |
| CN112803023B (en) | Lanthanum-zirconium-codoped high-nickel ternary cathode material and preparation method and application thereof | |
| CN112018378A (en) | Coating modification method for reducing metal dissolution of high-voltage ternary positive electrode material | |
| CN103280572B (en) | A kind of lithium ion cell positive ternary material and preparation method | |
| CN106129400A (en) | A kind of lanthanum part replaces spherical lithium-rich manganese-based anode material of manganese and preparation method thereof | |
| CN111769275A (en) | Doped high-voltage lithium cobalt oxide positive electrode material and preparation method thereof | |
| CN110085827A (en) | A kind of lithium-rich manganese-based anode material and its preparation method and application | |
| CN110350171A (en) | A kind of preparation method of the high ni-type tertiary cathode material of rubidium element doping | |
| CN106711416A (en) | Lithium-manganese-rich laminated anode material for lithium ion battery and preparation method thereof | |
| CN104733706B (en) | A kind of preparation method of high-tap density composite positive pole | |
| CN114655999A (en) | Method for regulating and controlling in-situ surface structure of lithium-rich layered oxide cathode material | |
| CN109037669A (en) | Modified nickel-cobalt lithium aluminate anode material and preparation method and application thereof | |
| CN117334857B (en) | Sodium ion battery positive electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190802 |
|
| RJ01 | Rejection of invention patent application after publication |