CN109004212A - A kind of big multiplying power manganate cathode material for lithium and preparation method thereof - Google Patents
A kind of big multiplying power manganate cathode material for lithium and preparation method thereof Download PDFInfo
- Publication number
- CN109004212A CN109004212A CN201810647107.3A CN201810647107A CN109004212A CN 109004212 A CN109004212 A CN 109004212A CN 201810647107 A CN201810647107 A CN 201810647107A CN 109004212 A CN109004212 A CN 109004212A
- Authority
- CN
- China
- Prior art keywords
- lithium
- multiplying power
- cathode material
- manganate
- big multiplying
- 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.)
- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 50
- 239000010406 cathode material Substances 0.000 title claims abstract description 34
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 41
- 239000011029 spinel Substances 0.000 claims abstract description 41
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims abstract description 32
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 32
- 238000005253 cladding Methods 0.000 claims abstract description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011572 manganese Substances 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 239000004005 microsphere Substances 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000011164 primary particle Substances 0.000 claims abstract description 4
- 238000000498 ball milling Methods 0.000 claims description 50
- 238000001354 calcination Methods 0.000 claims description 11
- 238000001694 spray drying Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910007913 Li-Al-Ti-P-O Inorganic materials 0.000 claims description 2
- 229910008474 Li—Al—Ti—P—O Inorganic materials 0.000 claims description 2
- 229910008291 Li—B—O Inorganic materials 0.000 claims description 2
- 229910007052 Li—Ti—O Inorganic materials 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920003169 water-soluble polymer Polymers 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 238000004513 sizing Methods 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 5
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 229910020734 Li0.3La0.56TiO3 Inorganic materials 0.000 description 20
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 229910010252 TiO3 Inorganic materials 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910009218 Li1.3Ti1.7Al0.3(PO4)3 Inorganic materials 0.000 description 1
- 229910010712 Li5La3Ta2O12 Inorganic materials 0.000 description 1
- 239000002225 Li5La3Ta2O12 Substances 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of big multiplying power manganate cathode material for lithium and preparation method thereof, and the positive electrode is by spinel lithium manganate and is coated between its primary particle and the solid electrolyte on second particle surface forms, and is porous microsphere shape.The preparation method is that: lithium source, manganese source are subjected to high-energy ball milling first, obtain spinel lithium manganate after subsequently heat-treated.Then the cladding for carrying out solid electrolyte is heat-treated after carrying out high-energy ball milling with solid electrolyte.By the LiMn2O4 after cladding and after high molecular polymer aqueous solution stirs and to form uniform sizing material, it is spray-dried, and be heat-treated and remove macromolecule to pore-creating, obtains the big multiplying power manganate cathode material for lithium.Solubility of the manganese in organic bath can be effectively reduced in the positive electrode, improve lithium ion conducting rate, have big circulation performance.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of big multiplying power manganate cathode material for lithium and its preparation
Method.
Background technique
Spinel lithium manganate LiMn2O4Positive electrode resourceful, low in cost, stable structure, safety with raw material manganese source
The advantages that property is high, is one of the anode material for lithium-ion batteries by favor.But the Mn due to LiMn2O4 on electric discharge latter stage surface3+
The high easily disproportionation of concentration generates the Mn for dissolving in electrolyte2+And electrolyte lithium salt LiPF6The a small amount of HF generated can corrode LiMn2O4
The loss for causing manganese element, so that capacity attenuation is very fast.In addition, the conductivity of LiMn2O4 is relatively low.The two is unfavorable for LiMn2O4
Big circulation.It is thus not applied for applying the lithium ion battery on electric car with fast charge at present for strategy.
There is research to coat spinel lithium manganate, the material coated has silica, aluminium oxide etc., so can be with
Inhibit the loss of manganese element, but the electric conductivity of these covering materials is poor, cannot provide good conductive environment.In recent years,
Solid electrolyte has obtained very big research.Some solid state electrolysis confrontation water oxygens are insensitive, can long-term existence in air, and
Lithium ion conducting rate is also considerable, also there is wider electrochemical window, provides new thinking to prepare electrode material.In
It is that people begin trying to coat one layer of solid electrolyte by sol-gal process on spinel lithium manganate；But colloidal sol is used merely
Gel method cladding solid electrolyte still has that energy density is not high.Meanwhile using merely using sol-gal process into
Row cladding, there is also certain problems when industrially applying.
Summary of the invention
The present invention is in view of the deficiencies of the prior art；A kind of manganate cathode material for lithium of big multiplying power porous microsphere shape is devised,
And a set of matched preparation method is devised simultaneously.
A kind of big multiplying power manganate cathode material for lithium of the present invention；The big multiplying power manganate cathode material for lithium is by spinel lithium manganate
LiMn2O4It is formed with solid electrolyte；The spinel lithium manganate LiMn2O4Primary particle between and second particle surface deposit
There is solid electrolyte, and is being porous microsphere shape.
In a kind of big multiplying power manganate cathode material for lithium of the invention, the mass fraction of solid electrolyte is 1%~6%.
A kind of big multiplying power manganate cathode material for lithium of the present invention；It is described by spinel lithium manganate LiMn2O4With solid state electrolysis texture
At porous microsphere partial size be 10-15 microns；Preferably 11.5-12.5 microns.
A kind of big multiplying power manganate cathode material for lithium of the present invention；The big multiplying power manganate cathode material for lithium is made with graphite
The Soft Roll of 3200mAh tests the discharge capacity of its 30C；Its discharge capacity is 2985mAh-3130mAh.Significantly larger than existing skill
Product in art.
A kind of preparation method of big multiplying power manganate cathode material for lithium of the present invention；The following steps are included:
Step 1
Ball milling cladding is carried out with solid state electrolysis confrontation spinel lithium manganate；It is heat-treated after ball milling；After being coated
Spinel lithium manganate；
Step 2
Spinel lithium manganate after cladding obtained by step 1 is mixed with high molecular polymer aqueous solution, slurrying；So
After be spray-dried, and be heat-treated and remove high molecular polymer to pore-creating, obtain the big multiplying power lithium manganate cathode material
Material.
A kind of preparation method of big multiplying power manganate cathode material for lithium of the present invention；The preparation method of the spinel lithium manganate
Are as follows: lithium source, manganese source are subjected to high-energy ball milling, obtain spinel lithium manganate after subsequently heat-treated.The revolving speed of the high-energy ball milling is
100~600rpm, Ball-milling Time are 12~28h.The heat treatment are as follows: under an oxygen-containing atmosphere, preferably under air atmosphere, in
400~1000 DEG C of 2~12h of calcining.Preferably, lithium source and manganese source press LiMn2O4Stoichiometric ratio ingredient.As into
The preferred embodiment of one step, the lithium source in the lithium compounds such as lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate at least one
Kind, manganese source uses manganese dioxide, manganese carbonate or manganese sesquioxide managnic oxide etc.,
A kind of preparation method of big multiplying power manganate cathode material for lithium of the present invention；In step 1, the solid electrolyte is selected from
La-Li-Ti-O system solid electrolyte (such as Li0.3La0.56TiO3), Li-Al-Ti-P-O system solid electrolyte (such as
Li1.3Ti1.7Al0.3(PO4)3), Li-La-Ta-O system solid electrolyte (such as Li5La3Ta2O12), Li-B-O system solid state electrolysis
Matter (such as 3Li2O-B2O3), Li-Ti-Zr-P-O system solid electrolyte (such as LiTi0.5Zr1.5(PO4)3) etc. stable in the air deposit
Oxide and at least one of phosphate system.
A kind of preparation method of big multiplying power manganate cathode material for lithium of the present invention；In step 1, when ball milling coats, ball milling is controlled
Revolving speed is 100~600rpm, and Ball-milling Time is 12~28h.
A kind of preparation method of big multiplying power manganate cathode material for lithium of the present invention；In step 1, after ball milling cladding, oxygenous
Under atmosphere, preferably under air atmosphere, in 400~1000 DEG C of 2~12h of calcining.Heat treatment i.e. after ball milling cladding are as follows: oxygenous
Under atmosphere, preferably under air atmosphere, in 400~1000 DEG C, preferably 700~850 DEG C of 2~12h of calcining.
A kind of preparation method of big multiplying power manganate cathode material for lithium of the present invention；In step 2, the high molecular polymer choosing
From at least one of water soluble polymers such as polyvinylpyrrolidone, carboxymethyl cellulose.
Preferably, in the aqueous solution of high molecular polymer described in step 2, the mass fraction of high molecular polymer is
0.05%~3%.
Preferably, by solid-liquid mass ratio, the ratio of 1:1.5-3, preferably 1:2 will coat obtained by step 1 in step 2
Spinel lithium manganate afterwards mixed with high molecular polymer aqueous solution, slurrying.
Preferably, the inlet temperature of spray drying is 200~350 DEG C in step 2, outlet temperature is 85~130 DEG C.
A kind of preparation method of big multiplying power manganate cathode material for lithium of the present invention；In step 2, the heat treatment are as follows: oxygen-containing
Under atmosphere, preferably under air atmosphere, in 400~1000 DEG C, preferably 700~850 DEG C of 2~12h of calcining.
Principle and advantage
The present invention devises a kind of manganate cathode material for lithium of big multiplying power porous microsphere shape for the first time；The big multiplying power LiMn2O4
Positive electrode is by spinel lithium manganate LiMn2O4It is formed with solid electrolyte；The spinel lithium manganate LiMn2O4Primary
There are solid electrolytes with second particle surface between grain, and are porous microsphere shape.
The present invention uses ball milling cladding for the first time and has prepared with high molecular polymer drying process with atomizing and has excellent performance
Product.It is realized between the primary particle of spinel lithium manganate using ball milling, spray drying and second particle surface coats
Solid electrolyte, and be porous microsphere shape.Solve the problems, such as that manganese element is lost in cyclic process, and improve lithium from
Subconductivity enhances big high rate performance.Preparation method is simple for this, is suitble to industrialization.Meanwhile it is optimized after, by each
The synergistic effect of preparation parameter, the discharge capacity for realizing 30C are up to 2985mAh-3130mAh, preferably 3000-3130mAh.
Product significantly larger than in the prior art.
Detailed description of the invention
Attached drawing 1 is embodiment 1-4 and comparative example 1, the discharge capacity of 2 products obtained therefrom 30C of comparative example detection figure.
Specific embodiment
Present invention ball-milling method and spray drying process prepare big multiplying power manganate cathode material for lithium.Below by specific implementation case
Example further illustrates.
Embodiment 1:
Firstly, lithium carbonate and manganese dioxide are pressed LiMn2O4Stoichiometric ratio weigh, then will be each with high speed ball mill
Raw material is mixed, ball milling speed 400rpm, Ball-milling Time 18h.Material after ball milling is put into crucible, in 500 DEG C
Keep the temperature 8h, natural cooling in furnace.Obtain spinel lithium manganate.
Further according to LiMn2O4Quality 5% weigh solid electrolyte Li0.3La0.56TiO3.By Li0.3La0.56TiO3With manganese
Sour lithium mixing, is mixed each raw material with high speed ball mill, ball milling speed 400rpm, Ball-milling Time 18h.After ball milling
Material be put into crucible, in natural cooling in 500 DEG C of heat preservation 4h, furnace.Obtain Li0.3La0.56TiO3The spinel manganese of cladding
Sour lithium.
By the Li of 500g0.3La0.56TiO3The carboxylic first that the spinel lithium manganate of cladding and the mass fraction of 1000g are 1.5%
Base cellulose aqueous solution mixes, by stirring to get uniform sizing material.Uniformly mixed slurry is subjected to spray drying treatment, is entered
Mouth temperature is 350 DEG C, and outlet temperature is 120 DEG C.By above-mentioned presoma in 800 DEG C of calcining 4h with remove carboxymethyl cellulose to
Pore-creating.Obtain Li0.3La0.56TiO3The spinel lithium manganate porous microsphere of cladding.3200mAh is made in institute's prepared material and graphite
Soft Roll, test the discharge capacity of its 30C, discharge capacity 3126.9mAh.
Embodiment 2:
Firstly, lithium carbonate and manganese dioxide are pressed LiMn2O4Stoichiometric ratio weigh, then will be each with high speed ball mill
Raw material is mixed, ball milling speed 100rpm, Ball-milling Time 28h.Material after ball milling is put into crucible, in 1000 DEG C
Keep the temperature 8h, natural cooling in furnace.Obtain spinel lithium manganate.
Further according to LiMn2O4Quality 1% weigh solid electrolyte Li0.3La0.56TiO3.By Li0.3La0.56TiO3With manganese
Sour lithium mixing, is mixed each raw material with high speed ball mill, ball milling speed 100rpm, Ball-milling Time 12h.After ball milling
Material be put into crucible, in natural cooling in 400 DEG C of heat preservation 12h, furnace.Obtain Li0.3La0.56TiO3The spinel manganese of cladding
Sour lithium.
By the Li of 500g0.3La0.56TiO3The carboxylic first that the spinel lithium manganate of cladding and the mass fraction of 1000g are 0.05%
Base cellulose aqueous solution mixes, by stirring to get uniform sizing material.Uniformly mixed slurry is subjected to spray drying treatment, is entered
Mouth temperature is 200 DEG C, and outlet temperature is 85 DEG C.By above-mentioned presoma in 400 DEG C of calcining 12h with remove carboxymethyl cellulose to
Pore-creating.Obtain Li0.3La0.56TiO3The spinel lithium manganate porous microsphere of cladding.3200mAh is made in institute's prepared material and graphite
Soft Roll, test the discharge capacity of its 30C, discharge capacity 2987.6mAh.
Embodiment 3:
Firstly, lithium carbonate and manganese dioxide are pressed LiMn2O4Stoichiometric ratio weigh, then will be each with high speed ball mill
Raw material is mixed, ball milling speed 600rpm, Ball-milling Time 12h.Material after ball milling is put into crucible, in 400 DEG C
Keep the temperature 4h, natural cooling in furnace.Obtain spinel lithium manganate.
Further according to LiMn2O4Quality 6% weigh solid electrolyte Li0.3La0.56TiO3.By Li0.3La0.56TiO3With manganese
Sour lithium mixing, is mixed each raw material with high speed ball mill, ball milling speed 600rpm, Ball-milling Time 28h.After ball milling
Material be put into crucible, in natural cooling in 1000 DEG C of heat preservation 3h, furnace.Obtain Li0.3La0.56TiO3The spinel manganese of cladding
Sour lithium.
By the Li of 500g0.3La0.56TiO3The carboxymethyl that the spinel lithium manganate of cladding and the mass fraction of 1000g are 3%
Cellulose aqueous solution mixes, by stirring to get uniform sizing material.Uniformly mixed slurry is subjected to spray drying treatment, entrance
Temperature is 350 DEG C, and outlet temperature is 130 DEG C.By above-mentioned presoma in 1000 DEG C of calcining 2h with remove carboxymethyl cellulose to
Pore-creating.Obtain Li0.3La0.56TiO3The spinel lithium manganate porous microsphere of cladding.3200mAh is made in institute's prepared material and graphite
Soft Roll, test the discharge capacity of its 30C, discharge capacity 2988.6mAh.
Embodiment 4:
Firstly, lithium carbonate and manganese dioxide are pressed LiMn2O4Stoichiometric ratio weigh, then will be each with high speed ball mill
Raw material is mixed, ball milling speed 400rpm, Ball-milling Time 20h.Material after ball milling is put into crucible, in 700 DEG C
Keep the temperature 7h, natural cooling in furnace.Obtain spinel lithium manganate.
Further according to LiMn2O4Quality 3.5% weigh solid electrolyte Li0.3La0.56TiO3.By Li0.3La0.56TiO3With
LiMn2O4 mixing, is mixed each raw material with high speed ball mill, ball milling speed 400rpm, Ball-milling Time 20h.By ball milling
Material afterwards is put into crucible, in natural cooling in 700 DEG C of heat preservation 7h, furnace.Obtain Li0.3La0.56TiO3The spinelle of cladding
LiMn2O4.
By the Li of 500g0.3La0.56TiO3The carboxylic first that the spinel lithium manganate of cladding and the mass fraction of 1000g are 1.5%
Base cellulose aqueous solution mixes, by stirring to get uniform sizing material.Uniformly mixed slurry is subjected to spray drying treatment, is entered
Mouth temperature is 275 DEG C, and outlet temperature is 108 DEG C.By above-mentioned presoma in 700 DEG C of calcining 7h with remove carboxymethyl cellulose to
Pore-creating.Obtain Li0.3La0.56TiO3The spinel lithium manganate porous microsphere of cladding.3200mAh is made in institute's prepared material and graphite
Soft Roll, test the discharge capacity of its 30C, discharge capacity 3078.4mAh.
Comparative example 1:
Lithium carbonate and manganese dioxide are pressed into LiMn2O4Stoichiometric ratio weigh, then with high speed ball mill by each raw material into
Row mixing, ball milling speed 400rpm, Ball-milling Time 20h.Material after ball milling is put into crucible, in 700 DEG C of heat preservation 7h,
Natural cooling in furnace.Obtain spinel lithium manganate.Institute's prepared material and graphite are made to the Soft Roll of 3200mAh, test its 30C's
Discharge capacity, discharge capacity 783.7mAh.
Comparative example 2
Lithium carbonate and manganese dioxide are pressed into LiMn2O4Stoichiometric ratio weigh, then with high speed ball mill by each raw material into
Row mixing, ball milling speed 400rpm, Ball-milling Time 20h.Material after ball milling is put into crucible, in 700 DEG C of heat preservation 7h,
Natural cooling in furnace.Obtain spinel lithium manganate.
Further according to LiMn2O4Quality 5% weigh solid electrolyte Li0.3La0.56TiO3.By Li0.3La0.56TiO3With manganese
Sour lithium mixing, is mixed each raw material with high speed ball mill, ball milling speed 400rpm, Ball-milling Time 18h.After ball milling
Material be put into crucible, in natural cooling in 500 DEG C of heat preservation 4h, furnace.Obtain Li0.3La0.56TiO3The spinel manganese of cladding
Sour lithium.
Institute's prepared material and graphite are made to the Soft Roll of 3200mAh, test the discharge capacity of its 30C, discharge capacity is only
1770.7mAh。
Claims (10)
1. a kind of big multiplying power manganate cathode material for lithium；It is characterized by: the big multiplying power manganate cathode material for lithium is by spinel manganese
Sour lithium LiMn2O4It is formed with solid electrolyte；The spinel lithium manganate LiMn2O4Primary particle between and second particle table
There are solid electrolytes in face, and are porous microsphere shape.
2. a kind of big multiplying power manganate cathode material for lithium according to claim 1, it is characterised in that: the big multiplying power LiMn2O4
The mass fraction of solid electrolyte is 1%~6% in positive electrode.
3. a kind of big multiplying power manganate cathode material for lithium according to claim 1, it is characterised in that: described by spinelle mangaic acid
Lithium LiMn2O4The partial size of the porous microsphere constituted with solid electrolyte is 10-15 microns.
4. a kind of big multiplying power manganate cathode material for lithium according to claim 1, it is characterised in that: by the big multiplying power mangaic acid
The Soft Roll of 3200mAh is made in lithium anode material and graphite, tests the discharge capacity of its 30C；Its discharge capacity is 2985mAh-
3130mAh。
5. a kind of preparation method of big multiplying power manganate cathode material for lithium described in -4 any one according to claim 1；Its feature exists
In；The following steps are included:
Step 1
Ball milling cladding is carried out with solid state electrolysis confrontation spinel lithium manganate；It is heat-treated after ball milling；Point after being coated is brilliant
Stone LiMn2O4；
Step 2
Spinel lithium manganate after cladding obtained by step 1 is mixed with high molecular polymer aqueous solution, slurrying；Then into
Row spray drying, and be heat-treated and remove high molecular polymer to pore-creating, obtain the big multiplying power manganate cathode material for lithium.
6. a kind of preparation method of big multiplying power manganate cathode material for lithium according to claim 5；It is characterized by: the point
Spar LiMn2O4 the preparation method comprises the following steps: by lithium source, manganese source carry out high-energy ball milling, obtain spinel lithium manganate after subsequently heat-treated；
The revolving speed of the high-energy ball milling is 100~600rpm, and Ball-milling Time is 12~28h；
The heat treatment are as follows: under an oxygen-containing atmosphere, in 400~1000 DEG C of 2~12h of calcining.
7. a kind of preparation method of big multiplying power manganate cathode material for lithium according to claim 5；It is characterized by: step 1
In, the solid electrolyte is selected from La-Li-Ti-O system solid electrolyte, Li-Al-Ti-P-O system solid electrolyte, Li-
La-Ta-O system solid electrolyte, Li-B-O system solid electrolyte, in Li-Ti-Zr-P-O system solid electrolyte at least
It is a kind of.
8. a kind of preparation method of big multiplying power manganate cathode material for lithium according to claim 5；It is characterized by:
In step 1, when ball milling coats, control rotational speed of ball-mill is 100~600rpm, and Ball-milling Time is 12~28h；
In step 1, after ball milling cladding, under an oxygen-containing atmosphere, in 400~1000 DEG C of 2~12h of calcining.
9. a kind of preparation method of big multiplying power manganate cathode material for lithium according to claim 5；It is characterized by: step 2
In, the high molecular polymer in the water soluble polymers such as polyvinylpyrrolidone, carboxymethyl cellulose extremely
Few one kind；
In the aqueous solution of high molecular polymer described in step 2, the mass fraction of high molecular polymer is 0.05%~3%.
In step 2, by solid-liquid mass ratio, 1:1.5-3 is by the spinel lithium manganate and high molecular polymerization after cladding obtained by step 1
Object aqueous solution mixed, slurrying.
10. a kind of preparation method of big multiplying power manganate cathode material for lithium according to claim 5；It is characterized by:
In step 2, the inlet temperature of spray drying is 200~350 DEG C, and outlet temperature is 85~130 DEG C；
In step 2, the heat treatment are as follows: under an oxygen-containing atmosphere, in 400~1000 DEG C of 2~12h of calcining.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810647107.3A CN109004212B (en) | 2018-06-22 | 2018-06-22 | High-rate lithium manganate positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810647107.3A CN109004212B (en) | 2018-06-22 | 2018-06-22 | High-rate lithium manganate positive electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109004212A true CN109004212A (en) | 2018-12-14 |
| CN109004212B CN109004212B (en) | 2020-10-20 |
Family
ID=64601056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810647107.3A Active CN109004212B (en) | 2018-06-22 | 2018-06-22 | High-rate lithium manganate positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109004212B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718910A (en) * | 2018-12-28 | 2019-05-07 | 中国科学院长春光学精密机械与物理研究所 | A kind of preparation method of the unordered nano material of refractory surfaces |
| CN111416111A (en) * | 2020-04-17 | 2020-07-14 | 中国科学院物理研究所 | Modified lithium manganate material, preparation method thereof and lithium battery |
| CN111640934A (en) * | 2020-04-18 | 2020-09-08 | 浙江金鹰新能源技术开发有限公司 | High-temperature solid-phase sintering method for lithium ion anode material |
| CN111934004A (en) * | 2020-08-19 | 2020-11-13 | 清陶（昆山）能源发展有限公司 | Lithium manganate/solid electrolyte composite material and preparation method and application thereof |
| CN114132966A (en) * | 2020-09-03 | 2022-03-04 | 星恒电源(滁州)有限公司 | Surface-modified lithium manganate material and preparation method thereof |
| CN114864940A (en) * | 2022-04-08 | 2022-08-05 | 中国科学院青岛生物能源与过程研究所 | High-mechanical-strength coating-layer-containing cathode material, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101841022A (en) * | 2010-05-13 | 2010-09-22 | 湘西自治州矿产与新材料技术创新服务中心 | Preparation method of lithium ion battery anode material lithium manganate |
| CN102088084A (en) * | 2009-12-03 | 2011-06-08 | 剩沅科技股份有限公司 | Lithium battery compound electrode active material and preparation method thereof |
| CN103700831A (en) * | 2012-09-28 | 2014-04-02 | 北京当升材料科技股份有限公司 | Preparation method of spherical lithium manganate material |
| CN106299339A (en) * | 2016-09-27 | 2017-01-04 | 中国科学院大学 | A kind of preparation method of lithium ion conductor coating spinelle manganate cathode material for lithium |
-
2018
- 2018-06-22 CN CN201810647107.3A patent/CN109004212B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102088084A (en) * | 2009-12-03 | 2011-06-08 | 剩沅科技股份有限公司 | Lithium battery compound electrode active material and preparation method thereof |
| CN101841022A (en) * | 2010-05-13 | 2010-09-22 | 湘西自治州矿产与新材料技术创新服务中心 | Preparation method of lithium ion battery anode material lithium manganate |
| CN103700831A (en) * | 2012-09-28 | 2014-04-02 | 北京当升材料科技股份有限公司 | Preparation method of spherical lithium manganate material |
| CN106299339A (en) * | 2016-09-27 | 2017-01-04 | 中国科学院大学 | A kind of preparation method of lithium ion conductor coating spinelle manganate cathode material for lithium |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718910A (en) * | 2018-12-28 | 2019-05-07 | 中国科学院长春光学精密机械与物理研究所 | A kind of preparation method of the unordered nano material of refractory surfaces |
| CN109718910B (en) * | 2018-12-28 | 2020-07-24 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of high-temperature-resistant surface disordered nano material |
| CN111416111A (en) * | 2020-04-17 | 2020-07-14 | 中国科学院物理研究所 | Modified lithium manganate material, preparation method thereof and lithium battery |
| CN111640934A (en) * | 2020-04-18 | 2020-09-08 | 浙江金鹰新能源技术开发有限公司 | High-temperature solid-phase sintering method for lithium ion anode material |
| CN111934004A (en) * | 2020-08-19 | 2020-11-13 | 清陶（昆山）能源发展有限公司 | Lithium manganate/solid electrolyte composite material and preparation method and application thereof |
| CN114132966A (en) * | 2020-09-03 | 2022-03-04 | 星恒电源(滁州)有限公司 | Surface-modified lithium manganate material and preparation method thereof |
| CN114864940A (en) * | 2022-04-08 | 2022-08-05 | 中国科学院青岛生物能源与过程研究所 | High-mechanical-strength coating-layer-containing cathode material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109004212B (en) | 2020-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109004212A (en) | A kind of big multiplying power manganate cathode material for lithium and preparation method thereof | |
| CN101855755B (en) | Li-Ni-based composite oxide particle powder for rechargeable battery with nonaqueous elctrolyte, process for producing the powder, and rechargeable battery with nonaqueous electrolyte | |
| CN106025254B (en) | A kind of surface coating modification method of nickel lithium manganate cathode material | |
| CN106299267B (en) | A kind of preparation method of titanium phosphate lithium titanate cathode material | |
| CN107403913A (en) | A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof | |
| CN101969110A (en) | Fast ion conductor modified lithium ion battery cathode material lithium cobalt oxide with fast ion conductor and preparation method | |
| CN105226267B (en) | Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application | |
| CN103151528A (en) | Method for preparing aluminum-doped zinc oxide coated lithium-ion battery positive-pole material | |
| CN108807920B (en) | LASO-coated octahedral-structure lithium nickel manganese oxide composite material and preparation method thereof | |
| CN104681808B (en) | Method for preparing strontium salt doped lithium nickel manganese oxide cathode material of lithium ion battery | |
| CN106571452A (en) | Lithium ion battery positive electrode material and preparation method thereof | |
| CN105633384B (en) | Power lithium-ion battery positive electrode surface modification technology method | |
| CN108172803A (en) | Cladded type richness lithium material that a kind of surface is modified and preparation method thereof and lithium ion battery | |
| CN105576218B (en) | A kind of step method dual modified to mangaic acid lithium doping, cladding | |
| CN109065871A (en) | It is a kind of to be mixed with modified nickel cobalt lithium aluminate cathode material and preparation method thereof | |
| CN102820459A (en) | Preparation method for synthesizing high-specific-energy lithium titanate material from mesoporous titanium dioxide | |
| CN109037649A (en) | It is a kind of to be mixed with modified nickel cobalt lithium aluminate cathode material and preparation method thereof | |
| CN103887496B (en) | A kind of preparation method of high performance lithium ion battery anode material LiMBO3C composite material | |
| CN108793254A (en) | A kind of Na0.7ZnxMnyO2The preparation method of stratified material | |
| CN108933247A (en) | A kind of simple method and product for preparing AZO and coating 523 monocrystalline nickel-cobalt-manganternary ternary anode materials | |
| CN106207150A (en) | A kind of atomizing freeze drying prepares the method for lithium cell negative pole material lithium titanate | |
| CN108899541B (en) | Magnesium lithium silicate coated modified lithium zinc titanate negative electrode material and preparation method thereof | |
| CN107507976A (en) | Composite mixed manganate cathode material for lithium of a kind of lithium aluminium boron and preparation method thereof | |
| CN110148712A (en) | A kind of rich lithium manganese anode material and preparation method thereof that compound coating is modified | |
| CN103367732A (en) | Carbon-coating method of negative electrode material of lithium ion secondary battery |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221117 Address after: 417009 North of East West Second Street and west of North South Third Road, Second Industrial Park, Economic and Technological Development Zone, Loudi City, Hunan Province Patentee after: HUNAN DIANJIANGJUN NEW ENERGY CO.,LTD. Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932 Patentee before: CENTRAL SOUTH University |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A high magnification lithium manganese oxide cathode material and its preparation method Granted publication date: 20201020 Pledgee: Bank of Communications Co.,Ltd. Loudi Branch Pledgor: HUNAN DIANJIANGJUN NEW ENERGY CO.,LTD. Registration number: Y2024980025287 |