CN105449202A - Method for preparing lithium iron phosphate positive electrode material by taking polycyclic aromatic hydrocarbon rein as carbon source - Google Patents
Method for preparing lithium iron phosphate positive electrode material by taking polycyclic aromatic hydrocarbon rein as carbon source Download PDFInfo
- Publication number
- CN105449202A CN105449202A CN201510796262.8A CN201510796262A CN105449202A CN 105449202 A CN105449202 A CN 105449202A CN 201510796262 A CN201510796262 A CN 201510796262A CN 105449202 A CN105449202 A CN 105449202A
- Authority
- CN
- China
- Prior art keywords
- iron phosphate
- hydrocarbon resin
- carbon source
- polyaromatic hydrocarbon
- lithium iron
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 68
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 58
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 39
- 239000007774 positive electrode material Substances 0.000 title abstract 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 69
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 33
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000013032 Hydrocarbon resin Substances 0.000 claims description 57
- 229920006270 hydrocarbon resin Polymers 0.000 claims description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000010792 warming Methods 0.000 claims description 22
- 239000005955 Ferric phosphate Substances 0.000 claims description 21
- 229940032958 ferric phosphate Drugs 0.000 claims description 21
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 238000009833 condensation Methods 0.000 claims description 14
- 230000005494 condensation Effects 0.000 claims description 14
- 125000003367 polycyclic group Chemical group 0.000 claims description 14
- 238000005453 pelletization Methods 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 239000000295 fuel oil Substances 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract 3
- 238000001035 drying Methods 0.000 abstract 2
- 229910000398 iron phosphate Inorganic materials 0.000 abstract 2
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 7
- 229930006000 Sucrose Natural products 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 229960004793 sucrose Drugs 0.000 description 7
- 229910052493 LiFePO4 Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000005720 sucrose Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- -1 polycyclic compound Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940006116 lithium hydroxide Drugs 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002912 waste gas Substances 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
- H01M4/58—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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a lithium iron phosphate positive electrode material by taking polycyclic aromatic hydrocarbon rein as a carbon source. The method comprises the steps of weighing iron phosphate and lithium hydroxide at the weight ratio of 1:3-5 firstly; uniformly mixing iron phosphate, lithium hydroxide and polycyclic aromatic hydrocarbon rein to obtain a mixture; adding the mixture into an ethanol solution and palletizing by adopting a wet process to obtain slurry containing ball-milled precursor; drying the slurry containing the ball-milled precursor in a drying oven, and pulverizing and screening the slurry to obtain a precursor; and finally putting the precursor into a high temperature furnace and performing thermal insulation to obtain the lithium iron phosphate positive electrode material. The carbon source adopted by the method is the polycyclic aromatic hydrocarbon rein, so that low temperature volatile component residue barely exists; the carbon content is more than 90wt%; the baking technological conditions have relatively less influences on a pyrolysis process, carbon residue rate and the like; and the obtained material is high in electrical property consistency.
Description
Technical field
The invention belongs to field of lithium ion battery, refer to that a kind of polyaromatic hydrocarbon resin that utilizes prepares the method for lithium iron phosphate positive material as carbon source particularly.
Background technology
Day by day serious in recent years along with energy shortage and problem of environmental pollution, country vigorously advocates energy-saving and emission-reduction and environmental protection, and the research and development of electric automobile (EV), hybrid electric vehicle (HEV) etc. are imperative.At present, can the bottleneck restricting Development of Electric Vehicles develop inexpensive, safe, eco-friendly secondary cell.Lithium ion battery, owing to having the feature such as high-energy-density and high-specific-power concurrently, is acknowledged as the most potential power battery of electric vehicle.The fail safe of lithium ion battery depends on positive electrode to a great extent.In various storage lithium anode material, LiFePO4 (LiFePO
4) security performance is good, have extended cycle life, raw material rich reserves, cheap, environmental friendliness, is applicable to jumbo electrokinetic cell.
It is its lower power density and poor consistency of performance that LiFePO 4 material applies restricted main cause.At present, with lower cost preparation in macroscopic quantity, there is high consistency, the LiFePO 4 material of high power density remains huge challenge.Technical research shows, the coated power density to LiFePO 4 material of carbon and consistency of performance play vital effect.Prepare carbon-coated LiFePO 4 for lithium ion batteries material and generally include the coated and coated two kinds of techniques of in-situ carbon of ex situ carbon.The former carries out separately the coated process of carbon on the lithium iron phosphate particles surface prepared, and normally carries out mechanical mixture with granulated carbon material; The latter adds organic carbon source, organic carbon source simultaneously cracking in the process of producing LiFePO4 thus to form carbon coated.
In the coated process of in-situ carbon, the usual solubilized of organic carbon source or melting, be easy to be coated on lithium iron phosphate particles surface, and meanwhile, organic carbon source plays the effect suppressing lithium iron phosphate particles to be grown up.Therefore in-situ carbon cladding process is widely adopted.
At present, application number be 201110154478.6 Chinese invention patent disclose a kind of preparation method of lithium iron phosphate/carbon composite material; This way utilizes oxalic acid and citric acid to prepare lithium iron phosphate/carbon composite material as carbon source; Application number be 201110023006.7 Chinese invention patent disclose a kind of wood fibre that utilizes and prepare the method for LiFePO4 as carbon source; Application number be 201010607952.1 Chinese invention patent disclose a kind of method for preparing solid phase of compound coating lithium iron phosphate positive material, the method utilizes citric acid to prepare compound coating lithium iron phosphate positive material as carbon source; Application number be 200810100457.4 Chinese invention patent disclose a kind of preparation method of LiFePO4; The method utilizes dextrose plus saccharose to prepare LiFePO4 as carbon source.The phosphorus content of above-mentioned carbon source is general lower; usually the decomposable process of series of complex can be there is in heating roasting process; and sintering temperature, roasting time, the kind of protection gas and the decomposable process of roasting technique condition on organic carbon source such as flow velocity, roasting sample size have appreciable impact, thus the LiFePO4 electrical property lot stability prepared is caused to be difficult to ensure.
Application number be 200810153980.3 Chinese invention patent disclose a kind of precursor used for coating iron phosphate lithium; The method utilizes pitch for carbon source, there is following defect:
1) component of pitch is very complicated, is a kind of very complicated mixture, and bituminous texture is unstable, and easily oxidized, run into its component of high temperature and also can change, the product stability of working it out is also very poor;
2) pitch has certain cementability, can be bonded on equipment in batch mixing process, is not easy to clean out;
3) pitch also in containing the element such as N, O, S, high temperature can produce SO
2gases such as (sulfur dioxide), contaminated environment, also has harm to human body.
Summary of the invention
The object of the invention is to solve prior art problem, adopt have high carbon content, low softening point polyaromatic hydrocarbon resin as carbon source; Provide a kind of method preparing lithium iron phosphate positive material.
For achieving the above object, a kind of polyaromatic hydrocarbon resin that utilizes provided by the invention prepares the method for lithium iron phosphate positive material as carbon source, comprises the following steps:
1) ferric phosphate and lithium hydroxide is taken by weight 1 ︰ 3 ~ 5; By ferric phosphate, lithium hydroxide and polyaromatic hydrocarbon resin, mix; Obtain mixture; Wherein, the weight of polyaromatic hydrocarbon resin accounts for 4 ~ 12% of the total addition of raw material
2) mixture is joined in ethanolic solution, carry out wet method pelletizing; Obtain the precursor pulp containing ball milling;
3) by step 2) precursor pulp obtained containing ball milling is placed in baking oven and dries, then carry out grinding and sieve and obtain presoma;
4) by step 3) prepare presoma and be placed in high temperature furnace, high temperature furnace by room temperature to 370 ~ 390 DEG C, and is incubated 1 ~ 3h under inert gas and temperature are 370 ~ 390 DEG C of conditions; Then 600 ~ 750 DEG C are warming up to from 370 ~ 390 DEG C; 8 ~ 15h is incubated again under temperature is 600-750 DEG C of condition inert gas; Namely lithium iron phosphate positive material is obtained.
Further, in described polyaromatic hydrocarbon resin, the content of heavy aromatics is 80 ~ 100%, carbon content >90%, and the temperature of softening point is: 100 ~ 200 DEG C.
Again further, the preparation method of described polyaromatic hydrocarbon resin, comprises the following steps:
1) using heavy aromatics in heavy oil residue as raw material, there is at least one in the compound of vinyl structure, phenol, aldehyde as crosslinking agent, under the effect of acidic catalyst and inorganic salt catalyst, carry out condensation reaction and generate B rank condensation polycyclic polynuclear aromatic resins;
2) B rank condensation polycyclic polynuclear aromatic resins is obtained C rank thermal endurance condensation polycyclic polynuclear aromatic resins through curing reaction.
Heavy aromatics is a kind of BTX aromatics, its composition relative complex, and the product often existing defects be synthesized with it with single crosslinking agent, because single crosslinking agent can only synthesize with a certain section in heavy aromatics.Use multiple crosslinking agent can with the different sections in heavy aromatics to carry out chemical synthesis, this makes it possible to prepare a kind of high softening-point, height is heat-resisting, condition of cure is gentle condensation polycyclic polynuclear aromatic resins.
In heavy aromatics of the present invention, low loop section (below 5 rings) and naphthols carry out chemical synthesis and generate many rings (more than 5 rings) compound; Multicyclic moeity is connected with harsh one-tenth polycyclic compound out by aziridine, generates the compound of more rings; Formaldehyde then can generate active methyl functional group on ring, makes solidification easier.This makes it possible to prepare a kind of high softening-point, height is heat-resisting, condition of cure is gentle condensation polycyclic polynuclear aromatic resins.
Again further, described step 2) in, the volume fraction of ethanolic solution is 50 ~ 100%; The time of pelletizing is 1 ~ 10h.
Again further, described step 3) in, the temperature of baking oven is 60 ~ 90 DEG C.
Again further, described step 4) in, the speed that temperature from ambient is warming up to 370 ~ 390 DEG C is 3 ~ 8 DEG C/min; Temperature is 3 ~ 8 DEG C/min by the speed that 370 ~ 390 DEG C are warming up to 600 ~ 750 DEG C.
Again further, described step 4) in, inert gas is nitrogen or argon gas.
Beneficial effect of the present invention is:
1, the present invention adopts carbon source polyaromatic hydrocarbon resin, hardly residual low temperature volatile component, and its carbon content rate is up to more than 90wt%, and roasting technique condition is less on impact such as its pyrolytic process, Residual carbon etc., and resulting materials electrical property consistency is good; Its carbon content rate is up to more than 90wt%, and the tail gas produced in roasting process will lack, more environmental protection; Polyaromatic hydrocarbon resin has self lubricity effect, can reduce material after baking and be bonded on equipment, decrease the maintenance to equipment, improve production efficiency; Polyaromatic hydrocarbon resin contains the heavy aromatics of 80 ~ 100%, is easy to obtain sp in the Process temperature ranges preparing lithium iron phosphate positive material
2the high conductivity carbon of hydridization, material is easy to obtain high power density; Preparation method's flow process is simple, and condition is easy to control, and production cost is low, thus has great actual application value.
2, in the production process of LiFePO 4 material, current enterprise generally adopts material that the carbon content rate such as sucrose (carbon content rate 42.10wt%), glucose (carbon content rate 36.24wt%) is low as carbon source, wherein the overwhelming majority is discharged with waste gas form, and a certain amount of solid fine particle can be taken out of, cause air pollution.The present invention is greater than the aromatic resins of 90wt% as carbon source using carbon content rate, and the discharge amount of exhaust gas in Material Manufacturing Process greatly reduces.The test data measuring and calculating current according to applying unit, often produce one ton of carbon-coated LiFePO 4 for lithium ion batteries material, when adopting sucrose to be carbon source, its discharge amount of exhaust gas is 288kg, and adopt carbon content rate its discharge amount of exhaust gas when the aromatic resins of more than 90wt% is carbon source to be significantly reduced to 95kg, namely discharge amount of exhaust gas reduces to 1/3 of original technique, decrease greenhouse gas emission and fine particulates pollution, energy-saving and emission-reduction effect is remarkable.
Accompanying drawing explanation
Fig. 1 is specific volume spirogram under polyaromatic hydrocarbon resin different proportion;
Fig. 2 is specific volume spirogram under polyaromatic hydrocarbon resin different temperatures;
Fig. 3 is the specific volume spirogram that polyaromatic hydrocarbon resin accounts for total amount 10%;
Fig. 4 is the specific volume spirogram that sucrose accounts for total amount 10%.
Embodiment
In order to explain the present invention better, illustrate main contents of the present invention further below in conjunction with specific embodiment, but content of the present invention is not only confined to following examples.
Utilize polyaromatic hydrocarbon resin to prepare a method for lithium iron phosphate positive material as carbon source, comprise the following steps:
1) ferric phosphate and lithium hydroxide is taken by weight 1 ︰ 3 ~ 5; By ferric phosphate, lithium hydroxide and polyaromatic hydrocarbon resin, mix; Obtain mixture; Wherein, the weight of polyaromatic hydrocarbon resin accounts for 4 ~ 12% of the total addition of raw material;
2) mixture is joined in ethanolic solution, carry out wet method pelletizing; Obtain the precursor pulp containing ball milling;
3) by step 2) precursor pulp obtained containing ball milling is placed in baking oven and dries, then carry out grinding and sieve and obtain presoma;
4) by step 3) prepare presoma and be placed in high temperature furnace, high temperature furnace by room temperature to 370 ~ 390 DEG C, and is incubated 1 ~ 3h under inert gas and temperature are 370 ~ 390 DEG C of conditions; Then 600 ~ 750 DEG C are warming up to from 370 ~ 390 DEG C; 8 ~ 15h is incubated again under temperature is 600 ~ 750 DEG C of condition inert gases; Namely lithium iron phosphate positive material is obtained.
In polyaromatic hydrocarbon resin, the content of heavy aromatics is 80 ~ 100%, carbon content >90%, and the temperature of softening point is: 100 ~ 200 DEG C.
The preparation method of polyaromatic hydrocarbon resin, comprises the following steps:
1) using heavy aromatics in heavy oil residue as raw material, there is at least one in the compound of vinyl structure, phenol, aldehyde as crosslinking agent, under the effect of acidic catalyst and inorganic salt catalyst, carry out condensation reaction and generate B rank condensation polycyclic polynuclear aromatic resins;
2) B rank condensation polycyclic polynuclear aromatic resins is obtained C rank thermal endurance condensation polycyclic polynuclear aromatic resins through curing reaction.
Described step 2) in, the volume fraction of ethanolic solution is 50 ~ 100%; The time of pelletizing is 1 ~ 10h.
Described step 3) in, the temperature of baking oven is 60 ~ 90 DEG C.
Described step 4) in, the speed that temperature from ambient is warming up to 370 ~ 390 DEG C is 3 ~ 8 DEG C/min; Temperature is 3 ~ 8 DEG C/min by the speed that 370 ~ 390 DEG C are warming up to 600 ~ 750 DEG C.
Described step 4) in, inert gas is nitrogen or argon gas.
Theoretical foundation of the present invention:
1) polyaromatic hydrocarbon resin is as the selection of the span of carbon source
(1) ferric phosphate and lithium hydroxide is taken by weight 1 ︰ 4, the polyaromatic hydrocarbon resin of Different Weight is mixed with ferric phosphate and lithium hydroxide respectively, obtain five groups of mixtures, wherein, the weight of polyaromatic hydrocarbon resin accounts for 4%, 6%, 8%, 10% and 12% of the total addition of raw material respectively;
(2) by five samples 1 ~ 5 that five groups of mixtures are prepared by following same procedure, concrete grammar is as follows:
Being added by mixture in 10ml ethanolic solution, is carry out wet method pelletizing 6h in 300r/min planetary ball mill at rotating speed; Then 80 DEG C of oven dry in baking oven, obtain presoma after grinding.The presoma prepared is placed in tube furnace, and under nitrogen protection, through 380 DEG C of insulation 1h, then be warming up to 650 DEG C of insulation 10h, roasting obtains sample 1 ~ 5
The above-mentioned sample 1 ~ 5 for preparing is carried out chemical property mensuration respectively, and concrete grammar is as follows:
85 ︰ 10 ︰ 5 take sample, conductive agent (acetylene black), binding agent (PTFE) in mass ratio, add 1-METHYLPYRROLIDONE, make it to mix and be shaped to flake, be washed into the positive pole diaphragm that diameter is 8mm after oven dry, and in vacuum drying chamber vacuumize 12h at 120 DEG C.Adopt lithium sheet for being barrier film to electrode, Celgard2400 polypropylene porous film, 1mol/LLiPF
6/ EC-EMC-DMC (1:1:1) is electrolyte assembly simulation battery.Blue electricity (LAND) battery test system (CT2001A) charge-discharge test instrument carries out different multiplying charge-discharge test to battery, and testing conditions is: under 25 DEG C of constant temperatures, and voltage range is 2.5 ~ 4.2V.Record the electric discharge result of material under 0.2C, 0.5C, 1C, 2C, 5C, 10C charge-discharge magnification as follows:
As can be seen from Figure 1, the consistency of carbon source is made with polyaromatic hydrocarbon resin all relatively good; Effect when the weight of polyaromatic hydrocarbon resin accounts for 4% of the total addition of raw material under low range is best; Effect when the weight of polyaromatic hydrocarbon resin accounts for 10% of the total addition of raw material under high magnification is best.
2) different temperatures roasting is on the impact of the chemical property of lithium iron phosphate positive material
(1) take ferric phosphate and lithium hydroxide by weight 1 ︰ 4, mixed with ferric phosphate, lithium hydroxide respectively by polyaromatic hydrocarbon resin, obtain mixture, wherein, the weight of polyaromatic hydrocarbon resin accounts for 4% of the total addition of raw material;
(2) being added by mixture in 10ml ethanolic solution, is carry out wet method pelletizing 6h in 300r/min planetary ball mill at rotating speed; Then 80 DEG C of oven dry in baking oven, obtain presoma after grinding.The presoma prepared is placed in tube furnace, and under nitrogen protection, through 380 DEG C of insulation 1h, then be warming up to 600 ~ 750 DEG C of insulation 10h, roasting obtains sample.
Under the prerequisite that said method is constant, then choose 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C four temperature in high temperature 600 ~ 750 DEG C of intervals respectively and carry out roasting, obtain sample a ~ d.
The above-mentioned sample a ~ d for preparing is carried out chemical property mensuration respectively, and concrete grammar is as identical in said method,
As can be drawn from Figure 2, in high temperature 600 ~ 750 DEG C of roastings, 650 DEG C of effects are best:
Embodiment 1
Utilize polyaromatic hydrocarbon resin to prepare a method for lithium iron phosphate positive material as carbon source, comprise the following steps:
1) ferric phosphate and lithium hydroxide is taken by weight 1 ︰ 4; By ferric phosphate, lithium hydroxide and polyaromatic hydrocarbon resin, mix; Obtain mixture; Wherein, the weight of polyaromatic hydrocarbon resin accounts for 4% of the total addition of raw material;
2) mixture is joined in ethanolic solution, in rotating speed 300r/min planetary ball mill, carry out wet method pelletizing 6h; Obtain the precursor pulp containing ball milling;
3) by step 2) to be placed in temperature be that 80 DEG C of baking ovens are dried to the precursor pulp obtained containing ball milling, then carry out grinding and sieve and obtain presoma;
4) by step 3) prepare presoma and be placed in high temperature furnace, under nitrogen protection, high temperature furnace is that 5 DEG C/min is warming up to 380 DEG C by room temperature with speed, under temperature is 380 DEG C of conditions, be incubated 1h; Then be that 5 DEG C/min is warming up to 650 DEG C from 380 DEG C with speed; 10h is incubated again under temperature is 650 DEG C of conditions; Namely lithium iron phosphate positive material 1 is obtained.
Embodiment 2
Utilize polyaromatic hydrocarbon resin to prepare the method for lithium iron phosphate positive material as carbon source, comprise the following steps:
1) ferric phosphate and lithium hydroxide is taken by weight 1 ︰ 4; By ferric phosphate, lithium hydroxide and polyaromatic hydrocarbon resin, mix; Obtain mixture; Wherein, the weight of polyaromatic hydrocarbon resin accounts for 10% of the total addition of raw material;
2) mixture is joined in ethanolic solution, in rotating speed 300r/min planetary ball mill, carry out wet method pelletizing 6h; Obtain the precursor pulp containing ball milling;
3) by step 2) to be placed in temperature be that 80 DEG C of baking ovens are dried to the precursor pulp obtained containing ball milling, then carry out grinding and sieve and obtain presoma;
4) by step 3) prepare presoma and be placed in high temperature furnace, under nitrogen protection, high temperature furnace is that 3 DEG C/min is warming up to 380 DEG C by room temperature with speed, under temperature is 380 DEG C of conditions, be incubated 1h; Then be that 3 DEG C/min is warming up to 650 DEG C from 380 DEG C with speed; 15h is incubated again under temperature is 650 DEG C of conditions; Namely lithium iron phosphate positive material 2 is obtained.
Gained lithium iron phosphate positive material 2 assembles 4 batteries, and chemical property is known after measured, and the consistency making carbon source with polyaromatic hydrocarbon resin is all relatively good; Effect best (see Fig. 3) when the weight of polyaromatic hydrocarbon resin accounts for 10% of the total addition of raw material under high magnification.
Embodiment 3
Utilize polyaromatic hydrocarbon resin to prepare the method for lithium iron phosphate positive material as carbon source, comprise the following steps:
1) ferric phosphate and lithium hydroxide is taken by weight 1 ︰ 4; By ferric phosphate, lithium hydroxide and polyaromatic hydrocarbon resin, mix; Obtain mixture; Wherein, the weight of polyaromatic hydrocarbon resin accounts for 6% of the total addition of raw material;
2) mixture is joined in ethanolic solution, in rotating speed 300r/min planetary ball mill, carry out wet method pelletizing 6h; Obtain the precursor pulp containing ball milling;
3) by step 2) to be placed in temperature be that 8 DEG C of baking ovens are dried to the precursor pulp obtained containing ball milling, then carry out grinding and sieve and obtain presoma;
4) by step 3) prepare presoma and be placed in high temperature furnace, under nitrogen protection, high temperature furnace is that 8 DEG C/min is warming up to 380 DEG C by room temperature with speed, under temperature is 380 DEG C of conditions, be incubated 3h; Then be that 5 DEG C/min is warming up to 700 DEG C from 380 DEG C with speed; 8h is incubated again under temperature is 700 DEG C of conditions; Namely lithium iron phosphate positive material 3 is obtained.
Embodiment 4
Utilize polyaromatic hydrocarbon resin to prepare the method for lithium iron phosphate positive material as carbon source, comprise the following steps:
1) ferric phosphate and lithium hydroxide is taken by weight 1 ︰ 3; By ferric phosphate, lithium hydroxide and polyaromatic hydrocarbon resin, mix; Obtain mixture; Wherein, the weight of polyaromatic hydrocarbon resin accounts for 8% of the total addition of raw material;
2) mixture is joined in ethanolic solution, in rotating speed 300r/min planetary ball mill, carry out wet method pelletizing 10h; Obtain the precursor pulp containing ball milling;
3) by step 2) to be placed in temperature be that 60 ~ 90 DEG C of baking ovens are dried to the precursor pulp obtained containing ball milling, then carry out grinding and sieve and obtain presoma;
4) by step 3) prepare presoma and be placed in high temperature furnace, under nitrogen protection, high temperature furnace is that 5 DEG C/min is warming up to 390 DEG C by room temperature with speed, under temperature is 390 DEG C of conditions, be incubated 1h; Then be that 3 DEG C/min is warming up to 750 DEG C from 390 DEG C with speed; 8h is incubated again under temperature is 750 DEG C of condition inert gases; Namely lithium iron phosphate positive material 4 is obtained.
Embodiment 5
Utilize polyaromatic hydrocarbon resin to prepare the method for lithium iron phosphate positive material as carbon source, comprise the following steps:
1) ferric phosphate and lithium hydroxide is taken by weight 1 ︰ 5; By ferric phosphate, lithium hydroxide and polyaromatic hydrocarbon resin, mix; Obtain mixture; Wherein, the weight of polyaromatic hydrocarbon resin accounts for 12% of the total addition of raw material;
2) mixture is joined in ethanolic solution, in rotating speed 300r/min planetary ball mill, carry out wet method pelletizing 5h; Obtain the precursor pulp containing ball milling;
3) by step 2) to be placed in temperature be that 90 DEG C of baking ovens are dried to the precursor pulp obtained containing ball milling, then carry out grinding and sieve and obtain presoma;
4) by step 3) prepare presoma and be placed in high temperature furnace, under nitrogen protection, high temperature furnace is that 5 DEG C/min is warming up to 370 DEG C by room temperature with speed, under temperature is 370 DEG C of conditions, be incubated 1h; Then be that 5 DEG C/min is warming up to 600 DEG C from 370 DEG C with speed; 15h is incubated again under temperature is 600 DEG C of condition inert gases; Namely lithium iron phosphate positive material 5 is obtained.
Comparative example 1
Contrast using sucrose as carbon source.Take weight ratio 1 ︰ 4 and take ferric phosphate and lithium hydroxide, sucrose weight is account for the total addition of raw material 10%, and adding 10ml ethanol is ball-milling medium, in planetary ball mill, 300r/min ball milling 6h, then 80 DEG C of oven dry in baking oven, obtain presoma after grinding.The presoma prepared is placed in tube furnace, and under nitrogen protection, through 380 DEG C of insulation 1h, then be warming up to 650 DEG C of insulation 10h, roasting obtains carbon-coated LiFePO 4 for lithium ion batteries positive electrode.Assemble 4 batteries by comparative example 1 gained carbon-coated LiFePO 4 for lithium ion batteries material, chemical property measures (see Fig. 4).
As can be seen from Figure 4, sucrose specific discharge capacity (5C) under high magnification shows poor consistency.
Said method Raw is purchased from market, and the volume fraction of ethanolic solution is 50 ~ 100%; In polyaromatic hydrocarbon resin, the content of heavy aromatics is 80 ~ 100%, carbon content >90%, and the temperature of softening point is: 100 ~ 200 DEG C.
The preparation method of polyaromatic hydrocarbon resin, comprises the following steps:
1) using heavy aromatics in heavy oil residue as raw material, there is at least one in the compound of vinyl structure, phenol, aldehyde as crosslinking agent, under the effect of acidic catalyst and inorganic salt catalyst, carry out condensation reaction and generate B rank condensation polycyclic polynuclear aromatic resins;
2) B rank condensation polycyclic polynuclear aromatic resins is obtained C rank thermal endurance condensation polycyclic polynuclear aromatic resins through curing reaction.
Other unspecified part is prior art.Although above-described embodiment is to invention has been detailed description; but it is only the present invention's part embodiment; instead of whole embodiment, people can also obtain other embodiments according to the present embodiment under without creative prerequisite, and these embodiments all belong to scope.
Claims (7)
1. utilize polyaromatic hydrocarbon resin to prepare a method for lithium iron phosphate positive material as carbon source, it is characterized in that: comprise the following steps:
1) ferric phosphate and lithium hydroxide is taken by weight 1 ︰ 3 ~ 5; By ferric phosphate, lithium hydroxide and polyaromatic hydrocarbon resin, mix; Obtain mixture; Wherein, the weight of polyaromatic hydrocarbon resin accounts for 4 ~ 12% of the total addition of raw material
2) mixture is joined in ethanolic solution, carry out wet method pelletizing; Obtain the precursor pulp containing ball milling;
3) by step 2) precursor pulp obtained containing ball milling is placed in baking oven and dries, then carry out grinding and sieve and obtain presoma;
4) by step 3) prepare presoma and be placed in high temperature furnace, high temperature furnace by room temperature to 370 ~ 390 DEG C, and is incubated 1 ~ 3h under inert gas and temperature are 370 ~ 390 DEG C of conditions; Then 600 ~ 750 DEG C are warming up to from 370 ~ 390 DEG C; 8 ~ 15h is incubated again under temperature is 600 ~ 750 DEG C of conditions; Namely lithium iron phosphate positive material is obtained.
2. polyaromatic hydrocarbon resin prepares the method for lithium iron phosphate positive material as carbon source according to claim 1, it is characterized in that: in described polyaromatic hydrocarbon resin, the content of heavy aromatics is 80 ~ 100%, carbon content >90%, and the temperature of softening point is: 100 ~ 200 DEG C.
3. according to claim 1 or 2, polyaromatic hydrocarbon resin prepares the method for lithium iron phosphate positive material as carbon source, it is characterized in that: the preparation method of described polyaromatic hydrocarbon resin, comprises the following steps:
1) using heavy aromatics in heavy oil residue as raw material, there is at least one in the compound of vinyl structure, phenol, aldehyde as crosslinking agent, under the effect of acidic catalyst and inorganic salt catalyst, carry out condensation reaction and generate B rank condensation polycyclic polynuclear aromatic resins;
2) B rank condensation polycyclic polynuclear aromatic resins is obtained C rank thermal endurance condensation polycyclic polynuclear aromatic resins through curing reaction.
4. polyaromatic hydrocarbon resin prepares the method for lithium iron phosphate positive material as carbon source according to claim 3, it is characterized in that: described step 2) in, the volume fraction of ethanolic solution is 50 ~ 100%; The time of pelletizing is 1 ~ 10h.
5. according to claim 1 or 2, polyaromatic hydrocarbon resin prepares the method for lithium iron phosphate positive material as carbon source, it is characterized in that: described step 3) in, the temperature of baking oven is 60 ~ 90 DEG C.
6. according to claim 1 or 2, polyaromatic hydrocarbon resin prepares the method for lithium iron phosphate positive material as carbon source, it is characterized in that: described step 4) in, the speed that temperature from ambient is warming up to 370 ~ 390 DEG C is 3 ~ 8 DEG C/min; Temperature is 3 ~ 8 DEG C/min by the speed that 370 ~ 390 DEG C are warming up to 600 ~ 750 DEG C.
7. polyaromatic hydrocarbon resin prepares the method for lithium iron phosphate positive material as carbon source according to claim 6, it is characterized in that: described step 4) in, inert gas is nitrogen or argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510796262.8A CN105449202B (en) | 2015-11-18 | 2015-11-18 | The method for preparing lithium iron phosphate positive material as carbon source using polyaromatic hydrocarbon resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510796262.8A CN105449202B (en) | 2015-11-18 | 2015-11-18 | The method for preparing lithium iron phosphate positive material as carbon source using polyaromatic hydrocarbon resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105449202A true CN105449202A (en) | 2016-03-30 |
| CN105449202B CN105449202B (en) | 2018-10-23 |
Family
ID=55559163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510796262.8A Active CN105449202B (en) | 2015-11-18 | 2015-11-18 | The method for preparing lithium iron phosphate positive material as carbon source using polyaromatic hydrocarbon resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105449202B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6139989A (en) * | 1995-02-21 | 2000-10-31 | Mitsubishi Pencil Co., Ltd. | Cathode formed of graphite/carbon composite for lithium ion secondary battery |
| CN1526178A (en) * | 2001-05-15 | 2004-09-01 | Fdk株式会社 | Nonaqueous electrolytic secondary battery and method of producing anode material thereof |
| CN101162776A (en) * | 2007-10-26 | 2008-04-16 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium iron phosphate suitable for high multiplying power electrokinetic cell and method for producing the same |
| CN101746742A (en) * | 2008-12-11 | 2010-06-23 | 中国电子科技集团公司第十八研究所 | Method for preparing lithium ion battery anode material spherical LiFePO4 |
| CN102453227A (en) * | 2010-10-26 | 2012-05-16 | 武汉保华石化新材料开发有限公司 | Preparation method for polycyclic aromatic hydrocarbon resin |
-
2015
- 2015-11-18 CN CN201510796262.8A patent/CN105449202B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6139989A (en) * | 1995-02-21 | 2000-10-31 | Mitsubishi Pencil Co., Ltd. | Cathode formed of graphite/carbon composite for lithium ion secondary battery |
| CN1526178A (en) * | 2001-05-15 | 2004-09-01 | Fdk株式会社 | Nonaqueous electrolytic secondary battery and method of producing anode material thereof |
| CN101162776A (en) * | 2007-10-26 | 2008-04-16 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium iron phosphate suitable for high multiplying power electrokinetic cell and method for producing the same |
| CN101746742A (en) * | 2008-12-11 | 2010-06-23 | 中国电子科技集团公司第十八研究所 | Method for preparing lithium ion battery anode material spherical LiFePO4 |
| CN102453227A (en) * | 2010-10-26 | 2012-05-16 | 武汉保华石化新材料开发有限公司 | Preparation method for polycyclic aromatic hydrocarbon resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105449202B (en) | 2018-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103346293B (en) | Lithium ion battery cathode material and its preparation method, lithium ion battery | |
| CN104143635B (en) | A kind of artificial plumbago negative pole material and preparation method thereof | |
| CN103078090B (en) | Lithium ion power battery composite cathode material and its preparation method | |
| CN102201576B (en) | Porous carbon in situ composite lithium iron phosphate cathode material and preparation method thereof | |
| CN102956894B (en) | A kind of preparation method of lithium iron phosphate material anode sheet | |
| CN108598395A (en) | The magnanimity preparation method of monodisperse silica/nitrogen-doped carbon composite Nano ball or microballoon | |
| CN108400313A (en) | A kind of method of the nickelic positive electrode of modifying super hydrophobicity lithium battery | |
| CN108054351A (en) | A kind of lithium ion battery, silicon-carbon cathode material used and preparation method thereof | |
| CN106803574B (en) | Anode material for lithium-ion batteries and its preparation method and application | |
| CN103311514A (en) | Preparation method of modified graphite negative material of lithium-ion battery | |
| CN109599524A (en) | Ion selectivity composite diaphragm and its preparation method and application | |
| CN103887474A (en) | Method for improving capacity and cyclic stability of lithium-sulfur battery cathode material | |
| CN110357100A (en) | A kind of method and application preparing carbon material using waste tire | |
| CN106505184A (en) | A kind of polynary coating modification lithium ion battery negative material and preparation method thereof | |
| CN115663157B (en) | Hard carbon composite material for lithium ion battery and preparation method thereof | |
| CN106887593A (en) | A kind of preparation method of cathode material for high capacity lithium ion battery | |
| CN107863504A (en) | A kind of preparation method of core shell structure Si-C composite material | |
| CN106252627A (en) | A kind of preparation method of cathode material of lithium-ion power battery | |
| CN107068998A (en) | Battery electrode containing conducting polymer/graphene and its preparation method and application | |
| CN108493452A (en) | It is a kind of to inhibit the aqueous binders of pole piece material expansion and lithium ion battery negative material and preparation method based on it | |
| CN103441278A (en) | Method for preparing carbon-coated lithium iron phosphate through microwave pyrolysis of ionic liquid | |
| CN102347513A (en) | High-performance aqueous lithium iron phosphate power battery and manufacture method thereof | |
| CN111370629B (en) | Preparation method of self-supporting functional interlayer of lithium-sulfur battery | |
| CN113285050A (en) | Li-M-X-based solid lithium battery anode and preparation method thereof | |
| CN109167104A (en) | A kind of room temperature sodium-sulphur battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| 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: Method for preparing lithium iron phosphate cathode material using polycyclic aromatic hydrocarbon resin as carbon source Effective date of registration: 20220819 Granted publication date: 20181023 Pledgee: Qingshan Branch of Wuhan Rural Commercial Bank Co.,Ltd. Pledgor: WUHAN BAOHUA PETROCHEMICAL NEW MATERIAL DEVELOPMENT Co.,Ltd. Registration number: Y2022420000264 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230407 Granted publication date: 20181023 Pledgee: Qingshan Branch of Wuhan Rural Commercial Bank Co.,Ltd. Pledgor: WUHAN BAOHUA PETROCHEMICAL NEW MATERIAL DEVELOPMENT Co.,Ltd. Registration number: Y2022420000264 |
|
| PC01 | Cancellation 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: Preparation of LiFePO4 cathode material using polycyclic aromatic hydrocarbons resin as carbon source Effective date of registration: 20230411 Granted publication date: 20181023 Pledgee: Qingshan Branch of Wuhan Rural Commercial Bank Co.,Ltd. Pledgor: WUHAN BAOHUA PETROCHEMICAL NEW MATERIAL DEVELOPMENT Co.,Ltd. Registration number: Y2023420000156 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| CP03 | Change of name, title or address |
Address after: 430081 No.10, zone B, South Urban Industrial Park, Gongren village, Qingshan District, Wuhan City, Hubei Province Patentee after: Wuhan Baohua New Materials Co.,Ltd. Country or region after: China Address before: 430081 No.10, zone B, South Urban Industrial Park, Gongren village, Qingshan District, Wuhan City, Hubei Province Patentee before: WUHAN BAOHUA PETROCHEMICAL NEW MATERIAL DEVELOPMENT Co.,Ltd. Country or region before: China |
|
| CP03 | Change of name, title or address |