CN107919473A - The preparation method of lithium ion battery electrode active material - Google Patents
The preparation method of lithium ion battery electrode active material Download PDFInfo
- Publication number
- CN107919473A CN107919473A CN201610881012.9A CN201610881012A CN107919473A CN 107919473 A CN107919473 A CN 107919473A CN 201610881012 A CN201610881012 A CN 201610881012A CN 107919473 A CN107919473 A CN 107919473A
- Authority
- CN
- China
- Prior art keywords
- lithium
- electrode active
- active material
- preparation
- ion battery
- 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
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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of preparation method of lithium ion battery electrode active material, including provides lithium source solution and metallic element source；By the lithium source solution and the metallic element source hybrid reaction；Reaction product is dried, obtains presoma；And it is heat-treated the presoma.The present invention also provides a kind of preparation method of lithium ion battery electrode active material, which is solid-phase synthesis, and the solid-phase synthesis is raw material mix stages include in a solvent being chemically reacted naphthalene lithium and metallic element source the step of.
Description
Technical field
The present invention relates to the preparation method of field of energy source materials, more particularly to lithium ion battery electrode active material.
Background technology
As the fast development and generalization of portable electronic product, the market demand of lithium ion battery are growing day by day.With
Traditional secondary battery is compared, and lithium ion battery has energy density is high, have extended cycle life, memory-less effect and environmental pollution are small etc.
Advantage.
The cathode and anode of lithium ion battery contain the reversible intercalation materials of li ions as active material respectively, wherein, cathode is lived
Property material than negative active core-shell material have higher potential.Common positive electrode active materials are mainly lithium transition-metal combined oxidation
Thing or lithium transition metal phosphates, such as cobalt acid lithium, LiMn2O4, binary material, ternary material, LiFePO4, phosphoric acid vanadium lithium, phosphoric acid
Manganese lithium and iron manganese phosphate for lithium etc., common negative active core-shell material are mainly carbon material, and such as graphite, in addition also has lithium transition-metal to answer
Close oxide, such as lithium titanate.
The synthetic method of above-mentioned lithium-transition metal composite oxide and lithium transition metal phosphates has solid-phase synthesis, water
Heat/solvent thermal reaction method, coprecipitation method and sol-gel synthesis method etc..Wherein solid-phase synthesis is industrial the most frequently used
Synthetic method, specifically by the presoma containing transition metal, such as oxide, carbonate or hydroxide and lithium source, such as carbon
Sour lithium or lithium hydroxide carry out mechanical mixture by ball milling, then high temperature sintering.However, presoma and lithium in this preparation method
Source is mixed in solid granulates aspect, is made uniformity of mixture poor, is caused synthetic product material property unstable.
The content of the invention
Based on this, it is necessary to solve the above problems, providing a kind of preparation method of lithium ion battery electrode active material.
A kind of preparation method of lithium ion battery electrode active material, including：
S1, there is provided lithium source solution and metallic element source, the lithium source solution include solvent and be dissolved in the solvent lithiumation it is thick
At least one of aromatic hydrocarbon ring and the derivative of lithiumation polycyclic aromatic hydrocarbon；
S2, which is mixed and reacted with the metallic element source；
S3, the reaction product of step S2 is dried, obtains presoma；And
S4, is heat-treated the presoma.
A kind of preparation method of lithium ion battery electrode active material, the preparation method are solid-phase synthesis, which closes
Into method raw material mix stages include by least one of derivative of lithiumation polycyclic aromatic hydrocarbon and lithiumation polycyclic aromatic hydrocarbon with
Metallic element source is chemically reacted in a solvent.
The present invention is closed at least one of derivative of lithiumation polycyclic aromatic hydrocarbon and lithiumation polycyclic aromatic hydrocarbon as solid phase
The lithium source used in, and chemistry is carried out instead when lithium source is mixed with other metallic element sources by the step S2
Should, lithium is mixed with metallic element source in molecular level, so as to ensure that reaction is more uniformly distributed in synthesis in solid state in step s 4
Segregation-free, obtained electrode active material performance are more preferable.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method of lithium ion battery electrode active material of the embodiment of the present invention；
Fig. 2 is the XRD test charts of lithium ion battery electrode active material of the embodiment of the present invention；
Fig. 3 is the embodiment of the present invention 1 and the voltage capacity curve comparison figure of the lithium ion battery of comparative example；
Fig. 4 is the embodiment of the present invention 1 and the cycle performance comparison diagram of the lithium ion battery of comparative example.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right with reference to the accompanying drawings and embodiments
The preparation method of lithium ion battery electrode active material of the present invention is further elaborated.It is it should be appreciated that described herein
Specific embodiment only to explain the present invention, be not intended to limit the present invention.
Referring to Fig. 1, the embodiment of the present invention provides the preparation method of a lithium ion battery electrode active material, including：
S1, there is provided lithium source solution and metallic element source, the lithium source solution include solvent and be dissolved in the solvent lithiumation it is thick
At least one of aromatic hydrocarbon ring and the derivative of lithiumation polycyclic aromatic hydrocarbon；
S2, which is mixed and reacted with the metallic element source；
S3, the reaction product of step S2 is dried, obtains presoma；And
S4, is heat-treated the presoma.
The lithium source is at least one of derivative of lithiumation polycyclic aromatic hydrocarbon and lithiumation polycyclic aromatic hydrocarbon.The lithiumation condensed ring
Aromatic hydrocarbon is the compound of lithium and polycyclic aromatic hydrocarbon.The derivative of the lithiumation polycyclic aromatic hydrocarbon and the lithiumation polycyclic aromatic hydrocarbon property
Similar, the derivative of the polycyclic aromatic hydrocarbon for example can be that the alkyl of halogen atom or 1~6 carbon substitutes in the polycyclic aromatic hydrocarbon
Hydrogen atom and the material that is formed, the derivative of the lithiumation polycyclic aromatic hydrocarbon is the derivative of the polycyclic aromatic hydrocarbon and the chemical combination of lithium
Thing.The general formula of the derivative of the lithiumation polycyclic aromatic hydrocarbon and lithiumation polycyclic aromatic hydrocarbon can write LiX, and wherein X represents described thick
At least one of aromatic hydrocarbon ring and the derivative of lithiumation polycyclic aromatic hydrocarbon.The phenyl ring quantity of the polycyclic aromatic hydrocarbon be preferably 2 to
4。
The lithiumation polycyclic aromatic hydrocarbon is preferably naphthalene lithium (LiC10H8), pyrene lithium (LiC16H10), luxuriant and rich with fragrance lithium (LiC14H10) and anthracene lithium
(LiC14H10At least one of).The solvent can dissolve the lithiumation polycyclic aromatic hydrocarbon, and the virtue of the lithiumation condensed ring for being dissolved
Fragrant hydrocarbon chemical stabilization.Such as the solvent of the naphthalene lithium can be tetrahydrofuran (THF), ethylene carbonate (EC), carbonic acid diethyl
At least one of ester (DEC), propene carbonate (PC), dimethyl carbonate (DMC) and hexane.Lithiumation condensed ring in the lithium source solution
The concentration of aromatic hydrocarbon is preferably 0.05 to 0.6mol/L.Such as when the lithium source solution is naphthalene lithium solution, the concentration of naphthalene lithium is
0.05 to 0.6mol/L.
In one embodiment, which can be prepared by following steps：
Naphthalene, is dissolved in the solvent by S11 in vacuum or protective atmosphere；And
S12, lithium metal is added into the solvent and is reacted with naphthalene, obtains the naphthalene lithium solution.
The step of lithium metal is reacted with naphthalene can carry out at normal temperatures and pressures, such as at 20 DEG C to 40 DEG C, 1 air
Pressure carries out.Addition of the naphthalene with lithium metal in a solvent can be determined by the concentration for the naphthalene lithium solution that needs obtain.Should
Molar ratio between naphthalene and lithium metal can be 1:1.
Other lithium source solution can be used to be prepared with the identical or different method of above-mentioned naphthalene lithium solution.
The metallic element source is determined that the electrode active material can be positive-active by the target electrode active material synthesized
Material or negative active core-shell material, can be specifically lithium-metal composite oxides (Li-M-O) and lithium metal composite phosphate (Li-N-
PO4At least one of).Metallic element M includes at least one of nickel, cobalt and manganese, can also wrap in certain embodiments
Include doped chemical.Metallic element N includes at least one of nickel, cobalt, manganese, iron and vanadium, can also wrap in certain embodiments
Include doped chemical.When the electrode active material is negative active core-shell material, which can also be Li-Ti-
O.The electrode active material has reversible charge-discharge performance, can make lithium ion in different potentials reversible insertion and abjection.
More specifically, which can be that crystal structure is а-NaFeO2Type layer structure, spinel-type
At least one of lithium-metal composite oxides and lithium metal composite phosphate of structure or olivine-type structure.
The chemical formula of the lithium-metal composite oxides for example can be LiFe1-yLyPO4, LiMn1-yLyPO4, LiV1-yLyPO4,
LiCo1-yLyPO4, LiFe1-yLy(PO4)1-kF3k, LiMn1-yLy(PO4)1-kF3k, LiCo1-yLy(PO4)1-kF3k, LiNi1-yLy
(PO4)1-kF3k, LiV1-yLy(PO4)1-kF3k, LiNi1-yLyPO4, LixNi1-yLyO2, LixCo1-yLyO2, LixMn1-yLyO2,
LixMn2-zLzO4, LixNii-nMnj-mLnRmO4, LixNii-nCoj-mLnRmO4, LixCoi-nMnj-mLnRmO4, LixNidCoeMnfLgO2And
LixNidCoeAlfLgO2At least one of.
0.1≤x≤1.1,0≤y in above-mentioned chemical formula<1, i+j=2,0≤m<0.2,0≤n<0.2,0<i-n<2,0<j-m
<2,0<d<1,0<e<1,0<f<1,0≤g≤0.2,0<k<1, d+e+f+g=1,0≤z<2, it is preferable that 0≤z<0.1,0.1<y<
0.5.Wherein, L and R is doped chemical, selected from alkali metal, alkali earth metal, the 13rd race's element, the 14th race's element, mistake
Cross the one or more in race's element and rare earth element, it is preferable that L and R be selected from Co, Ni, Mn, Cr, V, Ti, Sn, Cu, Al, Fe,
B, at least one of Sr, Ca, Nd, Ga and Mg.
It is further preferable that the positive electrode active materials are layer structure cobalt acid lithium (LiCoO2), LiMn2O4 (LiMnO2), nickel acid
Lithium (LiNiO2), lithium nickel cobalt manganese oxide, such as LiNi1/3Co1/3Mn1/3O2、LiNi0.4Co0.4Mn0.2O2、
LiNi0.6Mn0.2Co0.2O2、LiNi0.8Co0.1Mn0.1O2And LiNi0.7Co0.2Mn0.1O2, lithium manganate having spinel structure (LiMn2O4), point
Spar type Li, Ni, Mn oxide (LiNi0.5Mn1.5O4), LiFePO4 (LiFePO4), lithium manganese phosphate (LiMnPO4), phosphoric acid vanadium lithium
(LiVPO4), iron manganese phosphate for lithium (LiFe0.5Mn0.5PO4), cobalt phosphate lithium (LiCoPO4) and LiNiPO (LiNiPO4) in extremely
Few one kind, which can be lithium titanate (Li4Ti5O12)。
The metallic element source is the metallic element derived compound in addition to lithium in the electrode active material, for providing electricity
Metallic element in the active material of pole in addition to lithium.The metallic element source for example can be one or more metallic elements (such as iron,
One or more in cobalt, nickel, manganese, titanium, vanadium or other doped chemicals) hydroxide, carbonate, oxalates, phosphate and
At least one of acylate.
It is appreciated that step S2 is the step of solid-phase synthesis to be prepared to the reaction raw materials mixing of electrode active material,
The reaction raw materials are by depending on the electrode active material that needs to synthesize, when the reaction raw materials include other raw materials, step S2 into
One step includes mixing the lithium source solution, the metallic element source and other raw materials, and at least makes the lithium source solution and the metal
The step of element source is reacted.For example, when the electrode active material is lithium metal composite phosphate, which can be with
It is phosphate radical (PO4 3-) source, step S1 further comprise provide phosphoric acid root, step S2 further comprises the lithium source is molten
Liquid, the metallic element source and the phosphoric acid root hybrid reaction.The phosphoric acid root for example can be ferric phosphate, ammonium phosphate, di(2-ethylhexyl)phosphate
At least one of hydrogen ammonium and diammonium hydrogen phosphate.
It is preferably not aqueous with the metallic element source of the lithium source solution reaction, including Free water, absorption water and the crystallization water.More
Preferably, before step S2 is carried out, the step of further comprising the metallic element source being dried.The drying atmosphere is preferred
For vacuum or protective gas.The drying temperature is preferably smaller than 100 DEG C, such as is dried at 60 DEG C to 80 DEG C.
In step S2, the lithium source is chemically reacted with metallic element source in the solvent, which can
To carry out at normal temperatures and pressures, such as carried out under 20 DEG C to 40 DEG C, 1 atmospheric pressure.It is more highly preferred to, the reaction is in protection gas
Carried out in atmosphere.The protective atmosphere is preferably nitrogen or rare gas, such as argon gas.The lithium source solution is mixed with the metallic element source
After can pass through stir promote reaction carry out.The lithium source can be mixed stoichiometrically with metallic element source, i.e., according to final
Lithium is mixed with the molar ratio of metallic element in electrode active material.In preferential embodiment, which can be relative to this
Metallic element source stoichiometric excess, such as excessive 1%~5%.Step S2 is by script in solid phase synthesis method
Mechanical mixture is improved to chemically react, and lithium is mixed with metallic element source in molecular level, the forerunner being used in follow-up sintering
The mixing of lithium and metallic element is more uniformly not likely to produce segregation in body, so as to obtain the more preferable electrode active material of performance.
In step S3, the solvent is removed by dry, obtains the reaction product of the lithium source and metallic element source.
After step S3, further the product can be ground, refine solid granulates.The drying temperature is preferably smaller than 100 DEG C, example
Such as it is dried at 60 DEG C to 80 DEG C.
In step S4, the temperature of the heat treatment can be 500 DEG C to 900 DEG C.The heat treatment can under normal pressure into
OK, such as at 1 atmosphere pressure carry out.The heat treatment can carry out in atmosphere.In 500 DEG C to 900 DEG C of heat treatment time
Preferably 200 minutes to 720 minutes.Product cooled to room temperature after the heat treatment, is the electrode active material.
The embodiment of the present invention also provides a kind of preparation method of lithium ion battery electrode active material, which is solid
Phase synthesi, the solid-phase synthesis include as the lithiumation polycyclic aromatic hydrocarbon of lithium source and lithiumation condensed ring virtue in raw material mix stages
At least one of derivative of fragrant hydrocarbon is chemically reacted in a solvent with other metallic element sources in addition to lithium.
The present invention is closed at least one of derivative of lithiumation polycyclic aromatic hydrocarbon and lithiumation polycyclic aromatic hydrocarbon as solid phase
The lithium source used in, and chemistry is carried out instead when lithium source is mixed with other metallic element sources by the step S2
Should, lithium is mixed with metallic element source in molecular level, so as to ensure that reaction is more uniformly distributed in synthesis in solid state in step s 4
Segregation-free, obtained electrode active material performance are more preferable.
Embodiment 1：Positive electrode active materials LiNi1/3Co1/3Mn1/3O2Preparation
S1, by metallic element source Ni1/3Co1/3Mn1/3(OH)2It is placed in 60 DEG C of dry 12h in vacuum drying chamber；In glove box
0.5~0.74g naphthalenes are inside taken to be dissolved in tetrahydrofuran (THF), then (lithium is relative to metal for the lithium piece of addition stoichiometric excess
Excessive about 5% (molar ratio) of element source), under normal temperature and pressure stirring reaction 24 hours to 48 it is small when, form stable naphthalene lithium solution；
S2, takes the dried metallic element source Ni of 5g1/3Co1/3Mn1/3(OH)2It is added in above-mentioned naphthalene lithium solution and continuous
Stirring promotes the progress of reaction；
S3, it is dry to remove THF after complete reaction, obtain solid mixt；And
S4, after solid mixt is ground, is heat-treated at different temperatures respectively, first with 3 before the heat treatment
DEG C/solid mixt is heated to the heat treatment temperature by the heating rate of min from room temperature.The heat treatment temperature and time difference
For 500 DEG C of 200~300min of insulation, 600 DEG C, 700 DEG C, 800 DEG C and 900 DEG C keep the temperature 480~720min respectively.Tied in heat treatment
By the product cooled to room temperature of step S4 after beam.
Referring to Fig. 2, different temperatures is heat-treated obtained product does XRD tests respectively, test result is shown in this
The product of heat-treatment temperature range synthesis is LiNi1/3Co1/3Mn1/3O2, possess obvious layer structure, and crystalline phase is single, without miscellaneous
Phase, and crystallinity is raised and improved with temperature.
The LiNi that 800 DEG C are thermally treated resulting in1/3Co1/3Mn1/3O2Half-cell is assembled as positive electrode active materials.Positive plate
Middle use acetylene black is as conductive agent, and for PVDF as binding agent, the mass ratio of positive electrode active materials, acetylene black and PVDF is 8:1:
1, using metal lithium sheet as to electrode, with the LiPF of 1mol/L6/ EC+DMC+EMC (volume ratios 1:1:1) electrolyte is used as,
CR2032 type button cells are assembled into argon gas glove box, electrochemical property test is carried out to battery after standing 12h.Refer to figure
3, using the battery specific capacity of 0.1C electric current constant-current discharges as 152mAhg-1.Referring to Fig. 4, the battery is subjected to constant current with 1C electric currents
Charge and discharge cycles are tested, and battery discharge specific capacity is about 117mAhg after 50 circulations-1。
Comparative example
By lithium source lithium hydroxide and metallic element source Ni1/3Co1/3Mn1/3(OH)2When ball milling mixing 12 is small, obtains solid-state and mix
Compound；And
The solid mixt is heat-treated at 800 DEG C, programming rate is in the same manner as in Example 1 with soaking time, obtains
To positive electrode active materials LiNi1/3Co1/3Mn1/3O2。
The positive electrode active materials are assembled into CR2032 type button cells using method same as Example 1, stand 12h
Electrochemical property test is carried out to battery afterwards.Referring to Fig. 3, using the battery specific capacity of 0.1C electric current constant-current discharges as 145mAhg-1.Referring to Fig. 4, by the battery with 1C electric currents carry out constant current charge-discharge loop test, 50 times circulation after battery discharge specific capacity about
For 108mAhg-1.By contrast, it can be seen that, conventional solid method 1C 50 capacity retention ratios of current cycle are about 88%, and are utilized
50 capacity retention ratios of active material 1C current cycles of this method synthesis are more than 90%.
Embodiment 2：Positive electrode active materials LiFePO4Preparation
S1, ferric chloride solution is fully reacted with ammonium phosphate, adds buffer solution, adjusts pH value in 3-4 or so, reaction 5h
More than, washing two is arrived three times, up to FePO after 100 DEG C of dryings4Presoma, ferric chloride concn used are 0.5mol/L, ammonium phosphate
Concentration is 0.5mol/L, and iron chloride is 1 with ammonium phosphate molar ratio:1；0.38g naphthalenes are taken to be dissolved in tetrahydrofuran in glove box
(THF) in, the lithium piece (lithium is relative to the excessive about 2-3% (molar ratio) in metallic element source) of stoichiometric excess is then added, often
Under normal temperature and pressure stirring reaction 24 hours to 48 it is small when, form stable naphthalene lithium solution；
S2, by the FePO4Presoma be added in the naphthalene lithium solution of aforementioned stable and be stirred continuously promote reaction into
OK；
S3, it is dry to remove THF after complete reaction, obtain solid mixt；And
S4, when 700 DEG C of heat treatments 8 are small in nitrogen atmosphere after solid mixture is mixed with reducing agent, lives up to cathode
Property material LiFePO4, which can be carbon black, sucrose or glucose.
Embodiment 3：Negative active core-shell material Li4Ti5O12Preparation
S1, takes 1g naphthalenes to be dissolved in tetrahydrofuran (THF) in glove box, then adds the lithium piece of stoichiometric excess
(Ti：Li=1.22), under normal temperature and pressure stirring reaction 24 hours to 48 it is small when, form stable naphthalene lithium solution；
S2, by TiO2The progress for promoting reaction is mixed and is stirred continuously with naphthalene lithium solution；
S3, treats to react completely, dry to remove THF, obtains solid mixt；And
S4, Li is thermally treated resulting in for 700 DEG C by solid mixt in atmosphere4Ti5O12。
Embodiment described above only expresses the several embodiments of the present invention, its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention 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 the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (12)
1. a kind of preparation method of lithium ion battery electrode active material, including：
S1, there is provided lithium source solution and metallic element source, the lithium source solution include solvent and is dissolved in the lithiumation condensed ring virtue of the solvent
At least one of fragrant hydrocarbon and the derivative of lithiumation polycyclic aromatic hydrocarbon；
S2, which is mixed and reacted with the metallic element source；
S3, the reaction product of step S2 is dried, obtains presoma；And
S4, is heat-treated the presoma.
2. the preparation method of lithium ion battery electrode active material according to claim 1, it is characterised in that the lithiumation is thick
Aromatic hydrocarbon ring is naphthalene lithium, pyrene lithium, luxuriant and rich with fragrance at least one of lithium and anthracene lithium.
3. the preparation method of lithium ion battery electrode active material according to claim 1, it is characterised in that the lithium source is molten
Liquid includes solvent and the naphthalene lithium being dissolved in the solvent, which is selected from tetrahydrofuran, ethylene carbonate, diethyl carbonate, carbon
At least one of acid propylene ester, dimethyl carbonate and hexane.
4. the preparation method of lithium ion battery electrode active material according to claim 3, it is characterised in that the lithium source is molten
The concentration of naphthalene lithium is 0.05 to 0.6mol/L in liquid.
5. the preparation method of lithium ion battery electrode active material according to claim 1, it is characterised in that the electrode active
Property material is at least one of lithium-metal composite oxides and lithium metal composite phosphate.
6. the preparation method of lithium ion battery electrode active material according to claim 1, it is characterised in that the electrode active
Property material is that crystal structure is а-NaFeO2The lithium metal composite oxygen of type layer structure, spinel structure or olivine-type structure
At least one of compound and lithium metal composite phosphate.
7. the preparation method of lithium ion battery electrode active material according to claim 1, it is characterised in that metal member
Plain source is the derived compound of the metallic element in addition to lithium in the electrode active material.
8. the preparation method of lithium ion battery electrode active material according to claim 7, it is characterised in that metal member
Plain source is at least one of hydroxide, carbonate, oxalates, phosphate and acylate of the metallic element.
9. the preparation method of lithium ion battery electrode active material according to claim 1, it is characterised in that when the electrode
When active material is lithium metal composite phosphate, step S1 further comprises providing phosphoric acid root, and step S2 is further wrapped
Include the step of mixing in the lithium source solution, the metallic element source with the phosphoric acid root.
10. the preparation method of lithium ion battery electrode active material according to claim 1, it is characterised in that the step
S2 is carried out at normal temperatures and pressures.
11. the preparation method of lithium ion battery electrode active material according to claim 1, it is characterised in that the step
The heat treatment temperature of S4 is 500 DEG C to 900 DEG C.
12. a kind of preparation method of lithium ion battery electrode active material, which is solid-phase synthesis, its feature exists
In the solid-phase synthesis includes in the derivative of lithiumation polycyclic aromatic hydrocarbon and lithiumation polycyclic aromatic hydrocarbon in raw material mix stages
At least one is chemically reacted in a solvent with metallic element source.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610881012.9A CN107919473B (en) | 2016-10-09 | 2016-10-09 | Preparation method of lithium ion battery electrode active material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610881012.9A CN107919473B (en) | 2016-10-09 | 2016-10-09 | Preparation method of lithium ion battery electrode active material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107919473A true CN107919473A (en) | 2018-04-17 |
| CN107919473B CN107919473B (en) | 2020-05-12 |
Family
ID=61891593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610881012.9A Active CN107919473B (en) | 2016-10-09 | 2016-10-09 | Preparation method of lithium ion battery electrode active material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107919473B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785933A (en) * | 2019-04-04 | 2020-10-16 | 武汉大学 | Industrial production method of lithium alloy film material |
| CN112349989A (en) * | 2020-11-05 | 2021-02-09 | 武汉大学 | Method for repairing and regenerating waste lithium ion battery positive electrode active material and obtained regenerated positive electrode active material |
| CN112864360A (en) * | 2019-11-28 | 2021-05-28 | 珠海冠宇电池股份有限公司 | High-voltage positive pole piece and lithium ion secondary battery containing same |
| WO2022266886A1 (en) * | 2021-06-23 | 2022-12-29 | 宁德时代新能源科技股份有限公司 | Preparation method for sei membrane-like component additive, electrolyte, lithium ion battery, battery module, battery pack, and electric device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1690694A (en) * | 2004-04-30 | 2005-11-02 | 中国科学院物理研究所 | Reagent for lithiation reaction, preparation method and use thereof |
| CN105655577A (en) * | 2016-04-14 | 2016-06-08 | 哈尔滨工业大学 | Method for improving high-temperature solid-phase reaction of anode material of lithium ion battery by wet lithium mixing |
-
2016
- 2016-10-09 CN CN201610881012.9A patent/CN107919473B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1690694A (en) * | 2004-04-30 | 2005-11-02 | 中国科学院物理研究所 | Reagent for lithiation reaction, preparation method and use thereof |
| CN105655577A (en) * | 2016-04-14 | 2016-06-08 | 哈尔滨工业大学 | Method for improving high-temperature solid-phase reaction of anode material of lithium ion battery by wet lithium mixing |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785933A (en) * | 2019-04-04 | 2020-10-16 | 武汉大学 | Industrial production method of lithium alloy film material |
| CN112864360A (en) * | 2019-11-28 | 2021-05-28 | 珠海冠宇电池股份有限公司 | High-voltage positive pole piece and lithium ion secondary battery containing same |
| CN112349989A (en) * | 2020-11-05 | 2021-02-09 | 武汉大学 | Method for repairing and regenerating waste lithium ion battery positive electrode active material and obtained regenerated positive electrode active material |
| WO2022266886A1 (en) * | 2021-06-23 | 2022-12-29 | 宁德时代新能源科技股份有限公司 | Preparation method for sei membrane-like component additive, electrolyte, lithium ion battery, battery module, battery pack, and electric device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107919473B (en) | 2020-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103636038B (en) | Non-aqueous electrolyte battery positive active material, its manufacture method and use its non-aqueous electrolyte battery | |
| Bensalah et al. | Review on synthesis, characterizations, and electrochemical properties of cathode materials for lithium ion batteries | |
| US7135252B2 (en) | Lithium metal oxide electrodes for lithium cells and batteries | |
| Gong et al. | Synthesis and electrochemical performance of Li2CoSiO4 as cathode material for lithium ion batteries | |
| KR101473322B1 (en) | Cathode active material and cathode and lithium battery containing the material | |
| KR101705250B1 (en) | Cathode active material, and cathode and lithium battery containing the material | |
| KR100449073B1 (en) | Cathode material for lithium secondary batteries and method for manufacturing the Same | |
| CN102149641B (en) | Method for producing lithium manganate particle powder and nonaqueous electrolyte secondary battery | |
| US20080026292A1 (en) | Cathode materials for lithium battery having higher performance | |
| Zhu et al. | Increased cycling stability of Li4Ti5O12-coated LiMn1. 5Ni0. 5O4 as cathode material for lithium-ion batteries | |
| KR20080020087A (en) | Positive active material for a lithium secondary battery, method of preparing thereof, and lithium secondary battery coprising the same | |
| KR20100060362A (en) | Positive active material for a lithium secondary battery, method of preparing thereof, and lithium secondary battery comprising the same | |
| KR101977995B1 (en) | Positive electrode active material coated with boron compounds for lithium secondary battery and preparation method thereof | |
| KR101904896B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| JP2014058442A (en) | Method for producing lithium metal phosphate | |
| KR20020062012A (en) | Positive active material for lithium secondary battery and method of preparing same | |
| KR20110034592A (en) | Positive electrode active material for non-aqueous electrolyte secondary battery, method for production of positive electrode active material for non-aqueous electrolyte secondary battery, positive electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery | |
| Dong et al. | The effect of doping Mg2+ on the structure and electrochemical properties of Li3V2 (PO4) 3 cathode materials for lithium-ion batteries | |
| CN100371254C (en) | Boron-substituted lithium compounds, active electrode materials, batteries and electrochrome devices | |
| CN107919473A (en) | The preparation method of lithium ion battery electrode active material | |
| JP5663567B2 (en) | Positive electrode active material for lithium secondary battery, method for producing the same, and lithium secondary battery including the same | |
| JPH11507171A (en) | Positive electrode material for rechargeable electrochemical cell and method of making the same | |
| CN104603061A (en) | Method for preparing nanopowder of carbon-coated lithium metal phosphate | |
| US20020076486A1 (en) | Method of preparing positive active material for rechargeable lithium batteries | |
| JP4724912B2 (en) | Method for producing positive electrode active material and method for producing non-aqueous electrolyte 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 |
Effective date of registration: 20210701 Address after: E2-504, China Sensor Network International Innovation Park, 200-11 Linghu Avenue, Xinwu District, Wuxi City, Jiangsu Province, 214142 Patentee after: Wuxi Huarui Xinneng battery material Co.,Ltd. Address before: 100084 No. 1 Tsinghua Yuan, Beijing, Haidian District Patentee before: TSINGHUA University |
|
| TR01 | Transfer of patent right |