CN109786618A - A kind of high power environment-friendly type ferric phosphate lithium cell and preparation method thereof - Google Patents
A kind of high power environment-friendly type ferric phosphate lithium cell and preparation method thereof Download PDFInfo
- Publication number
- CN109786618A CN109786618A CN201910119360.6A CN201910119360A CN109786618A CN 109786618 A CN109786618 A CN 109786618A CN 201910119360 A CN201910119360 A CN 201910119360A CN 109786618 A CN109786618 A CN 109786618A
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- preparation
- active material
- graphite oxide
- positive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 33
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 26
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 26
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 26
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 62
- 239000010439 graphite Substances 0.000 claims abstract description 62
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007773 negative electrode material Substances 0.000 claims abstract description 33
- 239000005011 phenolic resin Substances 0.000 claims abstract description 33
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 33
- 239000007774 positive electrode material Substances 0.000 claims abstract description 24
- 229910052493 LiFePO4 Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000005253 cladding Methods 0.000 claims abstract description 13
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 5
- 238000010276 construction Methods 0.000 claims abstract 2
- 239000011230 binding agent Substances 0.000 claims description 37
- 239000010410 layer Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 33
- 239000010406 cathode material Substances 0.000 claims description 30
- 239000006258 conductive agent Substances 0.000 claims description 30
- 238000007789 sealing Methods 0.000 claims description 30
- 239000010405 anode material Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 14
- 229910010710 LiFePO Inorganic materials 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000009413 insulation Methods 0.000 claims description 14
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000004224 protection Effects 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 239000005030 aluminium foil Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000009434 installation Methods 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- 238000004804 winding Methods 0.000 claims description 7
- 239000012790 adhesive layer Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 230000007423 decrease Effects 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000013538 functional additive Substances 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- ZSYNKHJUSDFTCQ-UHFFFAOYSA-N [Li].[Fe].P(O)(O)(O)=O Chemical compound [Li].[Fe].P(O)(O)(O)=O ZSYNKHJUSDFTCQ-UHFFFAOYSA-N 0.000 claims 1
- LCDFWRDNEPDQBV-UHFFFAOYSA-N formaldehyde;phenol;urea Chemical compound O=C.NC(N)=O.OC1=CC=CC=C1 LCDFWRDNEPDQBV-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 5
- 229910021382 natural graphite Inorganic materials 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 238000005538 encapsulation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KWWDVIIKMNQADG-UHFFFAOYSA-N boric acid;difluoro oxalate Chemical compound OB(O)O.FOC(=O)C(=O)OF KWWDVIIKMNQADG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 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
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of high power environment-friendly type ferric phosphate lithium cells and preparation method thereof, the battery includes cylindrical shell, cover top portion is equipped with nut cap, safety valve is equipped with below nut cap, cylindrical housing interior constitutes battery accommodating space, the center of battery accommodating space is equipped with the positive plate for being curled into tubular, the positive electrode active material layer by lithium iron phosphate nano bar construction is coated on positive plate surface, negative electrode tab is equipped in positive plate interval to constitute cylindrical battery core, the surface of negative electrode tab is coated with the negative electrode active material layer being made of the graphite oxide coated through phenolic resin, positive pole ear is distributed between cylindrical battery core and nut cap, the negative lug for stretching out shape is equipped in the tail portion of negative electrode tab, power-off proof assembl is distributed on positive pole ear.In its preparation process, LiFePO4 is prepared using hydrothermal template process, and carry out cathode with the mode of phenolic resin cladding graphite oxide and be modified, improve the cycle performance of battery, there is good reliability and safety.
Description
Technical field
The present invention relates to battery technology field more particularly to a kind of high power environment-friendly type ferric phosphate lithium cell and its preparation sides
Method.
Background technique
The energy and environment are two serious problems that the mankind must face in 21 century, tap a new source of energy and clean and is renewable
The energy is most one of the technical field of decisive influence in world economy from now on.Lithium ion battery specific energy with higher is close
Degree, high battery operating voltage, the advantages that self-discharge rate is low, storage life is long can be widely applied to military, civil small-scale electricity
In device.
Just currently on the market from the point of view of generally existing lithium ion battery, the performance of performance and lithium ion battery material is close
Cut phase is closed.Therefore the development course of lithium ion battery specifically includes positive and negative electrode material along with the innovation and breakthrough of battery material
Material, electrolyte, diaphragm etc., wherein the influence to battery of positive and negative electrode material and electrolyte is maximum and Study on Li-ion batteries
Emphasis.
Olivine structure lithium iron phosphate (LiFePO4) possess good charge and discharge platform, high safety and the feature of environmental protection,
The advantages that fabulous reversible capacity and extremely excellent cycle performance, has obtained more and more concerns and research.Currently, it develops
Major obstacle be the conductivity problems of LiFePO 4 material, the problems such as material homogeneity problem and its tap density is low, therefore
Seeking the LiFePO4 active material that synthetic method is controllable, material properties is excellent has extremely important effect.
The main Types of lithium cell cathode material have carbon material negative pole and non-carbon negative material at present.In negative electrode material,
The research and use of graphite material are comparatively extensive, but graphite, there is also some disadvantages, its first charge-discharge is irreversible
Capacity is high, and graphite flake layer is easy to be caused to peel off by the total insertion of organic electrolyte, leads to capacity attenuation, and cycle performance weakens, body
Product specific capacity is low, therefore graphite is not suitable for directly as negative electrode material.By being modified processing to natural graphite, can be allowed to
With preferable cycle performance and lower reversible capacity, so that the modified graphite material of preparation be made to have both the excellent of price and performance
Gesture has good facilitation to application of the natural graphite in negative electrode material.
In the normal charge and discharge process of battery, due to the continuous destruction and production along with SEI film, the above generation gas
Reaction be inevitable in the battery, with the progress of charge and discharge cycles, the amount of gas accumulated in battery is more and more,
It causes inner pressure of battery to rise, brings hidden danger to the safety of battery.In order to avoid the caused safety accident that air pressure rises, generally
Safety valve can be arranged in lithium-ion-power cell on end cap, open when air pressure is more than predetermined threshold and carry out pressure release, however at present
The bad problem of the generally existing reliability of safety valve, therefore design a kind of safe and reliable battery structure, be very important.
Therefore, those skilled in the art is dedicated to developing a kind of high power environment-friendly type ferric phosphate lithium cell, and provides it
The preparation method of this kind of ferric phosphate lithium cell can provide excellent, safe and reliable working performance by the battery.
Summary of the invention
In view of the above drawbacks of the prior art, the technical problem to be solved by the present invention is to promote ferric phosphate lithium cell
Working performance.
It to achieve the above object, include cylinder the present invention provides a kind of high power environment-friendly type ferric phosphate lithium cell
Shell, the bottom of cylindrical shell is equipped with bottom insulation piece, and the top of cylindrical shell is equipped with the nut cap for constituting positive terminal, lid
Sealing ring is distributed between at the top of cap and cylindrical shell, is disposed with peace in the axial direction of cylindrical shell below nut cap
Full valve and top insulating trip；Cylindrical housing interior constitutes battery accommodating space, and the center of battery accommodating space, which is equipped with, to be curled into
The positive plate of tubular is coated with positive electrode active material layer, conducting agent layer and adhesive layer on positive plate surface, in positive plate outer room
Every being equipped with negative electrode tab to constitute cylindrical battery core, the bottom of cylindrical battery core is equipped with bottom insulation piece, applies on the surface of negative electrode tab
It is covered with negative electrode active material layer, conducting agent layer and adhesive layer, and between positive plate and negative electrode tab, outside negative electrode tab and cylinder
It is equipped with membrane layer between shell, positive pole ear is distributed between cylindrical battery core and nut cap, is equipped with and stretches in the tail portion of negative electrode tab
The negative lug of shape out is filled with power-type electrolyte between positive plate and negative electrode tab, it is anti-that power-off is distributed on positive pole ear
Quick-fried component, power-off proof assembl are screw thread solenoid valve, and when inside battery air pressure is excessive, the elastic slice in screw thread solenoid valve is pushed up
It opens, so that the high pressure gas of inside battery is discharged；After the air pressure decline of inside battery, work of the elastic slice in spring restoring force
With lower reset.
Further, safety valve includes valve body, sealing glueballs and thimble, and running through in valve body has bleed passage, bleed passage
It is inside provided with arcwall face, sealing glueballs is provided in bleed passage, sealing glueballs is close to arcwall face with closed valve, thimble setting
In the top of sealing glueballs, one end of thimble is puncture portion and offsets with sealing glueballs, and the other end of thimble is fixed part and solid
It is scheduled on the inner sidewall of bleed passage.
Further, bleed passage includes the upper cylindrical channel with the first radius and the lower cylinder with the second radius
Shape channel, wherein pass through arc-shaped changeover portion compatible with sealing glueballs between upper cylindrical channel and lower cylindrical channel
Connection.
Further, positive active material is lithium iron phosphate nano stick, and negative electrode active material is to coat through phenolic resin
Graphite oxide, membrane layer PP, PE and PP constitute three layers of composite diaphragm, power-type electrolyte be lithium salts, functional additive and
The mixed solution of organic solvent.
According to above structure, the present invention also provides a kind of preparation method of high power environment-friendly type ferric phosphate lithium cell, packets
Include following steps:
(1) preparation of anode material: with FeCl2·4H2O、(NH4)2HPO4And LiOH3H2O is raw material, passes through hydro-thermal method
It is prepared into flower pattern LiFePO4Nanometer rods as a positive electrode active material, are made viscous of PVDF and organic solvent N-Methyl pyrrolidone
Agent is tied, one or more of conductive agents in conductive black, electrically conductive graphite, carbon fiber, carbon nanotube is put into binder,
Add LiFePO4Nanometer rods obtain anode material after mixing；
(2) preparation of positive plate: being coated uniformly on the both side surface in positive pole aluminium foil collector other than tab for anode material,
After vacuum drying, after being compacted, being punched, positive plate is obtained；
(3) preparation of cathode material: using the concentrated sulfuric acid as oxidant, graphite oxide is prepared using Hummers method, uses phenolic resin
The mode of cladding is modified graphite oxide, to obtain negative electrode active material, with PVDF and organic solvent N- crassitude
Binder is made in ketone, puts into acetylene black as conductive agent in binder, adds modified graphite oxide, after mixing,
Obtain cathode material；
(4) preparation of negative electrode tab: being coated uniformly on the both side surface in cathode aluminum foil current collector other than tab for cathode material,
After vacuum drying, after being compacted, being punched, negative electrode tab is obtained；
(5) assembling of battery: after positive plate is coated with membrane layer, outside is subject to the cylindrical electricity of negative electrode tab winding composition
Cylindrical battery core is fitted into shell by core, and top insulating trip and bottom insulation piece, positive pole are installed in the both ends of cylindrical battery core
It is contacted after installation power-off proof assembl with nut cap on ear, negative lug is contacted with shell, is electrolysed to interior of shell injecting power type
Liquid stands, encapsulation, battery is made.
Further, LiFePO4Nanometer rods are prepared according to the following steps: first by FeCl2·4H2O is dissolved in deionized water
In, (NH is added later4)2HPO4, and be stirred continuously and occur until blackish green precipitates, presoma Fe is obtained after being centrifuged off solution3
(PO4)2(H2O)8；Later by LiOH3H2O is dissolved in deionized water, and citric acid is added to adjust the pH value of solution to 2.5-
3.5, it is stirring evenly and then adding into presoma, continuing stirring dissolves presoma and be uniformly mixed with solution；Mixed solution is turned again
Enter filled with N2Autoclave, 180 DEG C of temperature heating for 24 hours, then centrifuge washing precipitating and at 60 DEG C it is drying precipitated for 24 hours
To LiFePO4Head product；Finally containing 5%H again2Ar in calcine head product 10h, calcination temperature is selected as 500-650 DEG C, finally
Obtain LiFePO4Nanometer rods.
Further, graphite oxide is prepared according to the following steps: weighing natural graphite and carries out in the agate mortar sufficiently
It is put into the beaker for filling the concentrated sulfuric acid, is placed on magnetic stirring apparatus after grinding, 1h is at the uniform velocity stirred at normal temperature, later at 60 DEG C
Continue to stir 4-6h in water-bath, then the solution being stirred is washed repeatedly with distilled water, place into and dry 12h in baking oven, it will
It completes dry material to be put into high-temperature tubular sintering furnace, is passed through N2200 DEG C are risen to the heating rate of 10 DEG C/min, heat preservation
1h is continuously heating to 600-700 DEG C of calcining at constant temperature 6h, obtains graphite oxide after cooling.
Further, phenolic resin cladding graphite oxide negative electrode active material the preparation method comprises the following steps: according to graphite oxide
The ratio of the 10-20% of quality weighs phenolic resin, is dissolved in dehydrated alcohol, and graphite oxide is added, using magnetic agitation 4-
6h is sufficiently mixed in dehydrated alcohol to graphite oxide and phenolic resin, and the container equipped with mixing liquid is put into 60-70 DEG C
Evaporative removal dehydrated alcohol in water-bath, then dries 10h in drying box, and the material that drying obtains is put into high-temperature tubular burning
In freezing of a furnace, in N2Under the protection of atmosphere, 200 DEG C are risen to the heating rate of 10 DEG C/min, 1h is kept the temperature, is continuously heating to 600-
700 DEG C of calcining 6h obtain the negative electrode active material of phenolic resin cladding graphite oxide after cooling.
Further, in anode material each component weight percentage are as follows: positive active material 80-90%, binder 5-
10%, conductive agent 5-10%；The weight percentage of each component in cathode material are as follows: negative electrode active material 80-90%, binder 5-
10%, conductive agent 5-10%.
Further, the surface density of positive plate is 250-280, compacted density 1.8-2.0；The surface density of negative electrode tab is
100-130, compacted density 1.1-1.3.
Technical effect:
(1) the shortcomings that present invention is prepared LiFePO4, overcome traditional preparation methods using hydrothermal template process, preparation method
Simple and easy, material morphology is controllable, and tap density is big, and cycle performance is excellent；
(2) main material present invention employs natural graphite as negative electrode active material, and coated with phenolic resin
Mode is modified, and organic solvent can effectively be prevented to contact with the direct of graphite flake layer, improves its cycle performance, impedance becomes
Small, irreversible capacity reduces；
(3) present invention uses screw thread solenoid valves as proof assembl, and provides the reusable safety improved
Valve can guarantee there is good reliability and safety in the battery long-term use process, also extend service life.
It is described further below with reference to technical effect of the attached drawing to design of the invention, specific structure and generation, with
It is fully understood from the purpose of the present invention, feature and effect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of high power environment-friendly type ferric phosphate lithium cell of the invention.
Fig. 2 is the structural schematic diagram of the safety valve of high power environment-friendly type ferric phosphate lithium cell of the invention.
In figure, 1 shell, 2 bottom insulation pieces, 3 nut caps, 4 sealing rings, 5 safety valves, 51 valve bodies, 52 sealing glueballs, 53 tops
Needle, 531 thimble main bodys, 532 puncture portions, 533 fixed parts, 54 bleed passages, 541 arcwall faces, cylindrical channel on 542, under 543
Cylindrical channel, 6 top insulating trips, 7 positive plates, 8 negative electrode tabs, 9 membrane layers, 10 positive pole ears, 11 negative lugs, 12 power-off are anti-
Quick-fried component.
Specific embodiment
As shown in Figure 1 it is a kind of high power environment-friendly type ferric phosphate lithium cell provided by the invention, includes the outer of cylinder
Shell 1, the bottom of cylindrical shell 1 are equipped with bottom insulation piece 2, and the top of cylindrical shell 1 is equipped with the nut cap 3 for constituting positive terminal,
Be distributed with sealing ring 4 between nut cap 3 and the top of cylindrical shell 1,3 lower section of nut cap along in the axial direction of cylindrical shell 1 successively
It is provided with safety valve 5 and top insulating trip 6.
1 Inner Constitution battery accommodating space of cylindrical shell, the center of battery accommodating space, which is equipped with, is being curled into tubular just
Pole piece 7 is coated with positive electrode active material layer, conducting agent layer and adhesive layer on 7 surface of positive plate, sets in 7 interval of positive plate
There is negative electrode tab 8 to constitute cylindrical battery core, the bottom of cylindrical battery core is equipped with bottom insulation piece 2, coats on the surface of negative electrode tab 8
There are negative electrode active material layer, conducting agent layer and adhesive layer, and between positive plate 7 and negative electrode tab 8, negative electrode tab 8 and cylinder
Membrane layer 9 is equipped between shell 1.Positive pole ear 10 is distributed between cylindrical battery core and nut cap 3, in the tail of negative electrode tab 8
Portion is equipped with the negative lug 11 for stretching out shape, and power-type electrolyte is filled between positive plate 7 and negative electrode tab 8.
The positive active material that above-mentioned ferric phosphate lithium cell of the invention is selected is lithium iron phosphate nano stick, negative electrode active material
Matter is the graphite oxide coated through phenolic resin, and membrane layer 9 is three layers of composite diaphragm that PP, PE and PP are constituted, power-type electrolysis
Liquid is the mixed solution of lithium salts, functional additive and organic solvent, lithium salts therein be selected from LiBF4, lithium hexafluoro phosphate,
Lithium perchlorate, two (fluorine sulphonyl) imine lithiums, two (trifluoromethane sulfonic acid acyl) imine lithiums, di-oxalate lithium borate, difluoro oxalate boric acid
The composition of one or more of lithium.
Power-off proof assembl 12 is distributed on positive pole ear 10, power-off proof assembl 12 is screw thread solenoid valve, in battery
When portion's air pressure is excessive, the elastic slice in screw thread solenoid valve is opened, so that the high pressure gas of inside battery is discharged；When in battery
After the air pressure decline in portion, elastic slice resets under the action of spring restoring force.
Safety valve 5 is as shown in Fig. 2, include valve body 51, sealing glueballs 52 and thimble 53, running through in valve body 51 has bleed passage
54, arcwall face 541 is provided in bleed passage 54, sealing glueballs 52 is provided in bleed passage 54, and sealing glueballs 52 is close to arc
With closed valve 51, thimble 53 is set to the top of sealing glueballs 52 in shape face 541, one end of thimble 53 be puncture portion and with sealing
Glueballs 52 offsets, and the other end of thimble 53 is fixed part and the inner sidewall for being fixed on bleed passage 54.Bleed passage 54 includes tool
There are the upper cylindrical channel 542 of the first radius and the lower cylindrical channel 543 with the second radius, wherein upper cylindrical channel
By being connect with the sealing compatible arc-shaped changeover portion of glueballs 52 between 542 and lower cylindrical channel 543.Thimble 53 includes top
Needle main body 531, puncture portion 532 and fixed part 533；Puncture portion 532 is located at one end of thimble main body 531, and puncture portion 532 is circle
Taper, fixed part 533 are located at the other end of thimble main body 531, and fixed part 533 is circle compatible with upper cylindrical channel 542
Cylindricality is provided with several ventholes on fixed part 533.
The course of work of above-mentioned safety valve: sealing glueballs can be maintained at sealing position under normal barometric pressure state by thimble
It sets, guarantees the overall sealing performance of lithium battery, it is ensured that the normal use of lithium battery.And under improper high pressure conditions, sealing
Glueballs can enter in puncture portion under stress, be detached from sealing station to realize the high pressure release of lithium battery.It is discharged in high pressure
Afterwards, thimble is pushed again, after so that sealing glueballs is reset to the sealing station, that is, can ensure that continuing to use for lithium battery.
The present invention also provides the preparation methods of above-mentioned high power environment-friendly type ferric phosphate lithium cell, specifically include following step
It is rapid:
(1) preparation of anode material: with FeCl2·4H2O、(NH4)2HPO4And LiOH3H2O is raw material, passes through hydro-thermal method
It is prepared into flower pattern LiFePO4Nanometer rods as a positive electrode active material, are made viscous of PVDF and organic solvent N-Methyl pyrrolidone
Agent is tied, one or more of conductive agents in conductive black, electrically conductive graphite, carbon fiber, carbon nanotube is put into binder,
Add LiFePO4Nanometer rods obtain anode material after mixing；Preferably, in anode material each component weight percentage
Are as follows: positive active material 80-90%, binder 5-10%, conductive agent 5-10%；
(2) preparation of positive plate: being coated uniformly on the both side surface in positive pole aluminium foil collector other than tab for anode material,
After vacuum drying, after being compacted, being punched, positive plate is obtained, the surface density of positive plate is 250-280, compacted density 1.8-
2.0；
(3) preparation of cathode material: using the concentrated sulfuric acid as oxidant, graphite oxide is prepared using Hummers method, uses phenolic resin
The mode of cladding is modified graphite oxide, to obtain negative electrode active material, with PVDF and organic solvent N- crassitude
Binder is made in ketone, puts into acetylene black as conductive agent in binder, adds modified graphite oxide, after mixing,
Obtain cathode material；Preferably, in cathode material each component weight percentage are as follows: negative electrode active material 80-90%, binder 5-
10%, conductive agent 5-10%；
(4) preparation of negative electrode tab: being coated uniformly on the both side surface in cathode aluminum foil current collector other than tab for cathode material,
After vacuum drying, after being compacted, being punched, negative electrode tab is obtained, the surface density of negative electrode tab is 100-130, compacted density 1.1-
1.3；
(5) assembling of battery: after positive plate is coated with membrane layer, outside is subject to the cylindrical electricity of negative electrode tab winding composition
Cylindrical battery core is fitted into shell by core, and top insulating trip and bottom insulation piece, positive pole are installed in the both ends of cylindrical battery core
It is contacted after installation power-off proof assembl with nut cap on ear, negative lug is contacted with shell, is electrolysed to interior of shell injecting power type
Liquid stands, encapsulation, battery is made.
LiFePO is prepared according to the following steps4Nanometer rods: first by FeCl2·4H2O is dissolved in deionized water, is added later
(NH4)2HPO4, and be stirred continuously and occur until blackish green precipitates, presoma Fe is obtained after being centrifuged off solution3(PO4)2(H2O)8；
Later by LiOH3H2O is dissolved in deionized water, and citric acid is added to adjust the pH value of solution to 2.5-3.5, after mixing evenly
Presoma is added, continuing stirring dissolves presoma and be uniformly mixed with solution；Mixed solution is transferred to filled with N again2High pressure
Kettle, 180 DEG C of temperature heating for 24 hours, then centrifuge washing precipitating and drying precipitated at 60 DEG C obtain LiFePO for 24 hours4Primiparity
Object；Finally containing 5%H again2Ar in calcine head product 10h, calcination temperature is selected as 500-650 DEG C, finally obtains LiFePO4It receives
Rice stick.
Graphite oxide is prepared according to the following steps: weighing after natural graphite is fully ground in the agate mortar and is put into
It fills in the beaker of the concentrated sulfuric acid, is placed on magnetic stirring apparatus, at the uniform velocity stir 1h at normal temperature, continue in 60 DEG C of water-bath later
4-6h is stirred, then the solution being stirred is washed repeatedly with distilled water, is placed into and dry 12h in baking oven, drying will be completed
Material is put into high-temperature tubular sintering furnace, is passed through N2200 DEG C are risen to the heating rate of 10 DEG C/min, 1h is kept the temperature, continues to heat up
To 600-700 DEG C of calcining at constant temperature 6h, graphite oxide is obtained after cooling.
Phenolic resin coat graphite oxide negative electrode active material the preparation method comprises the following steps: according to graphite oxide quality 10-
20% ratio weighs phenolic resin, is dissolved in dehydrated alcohol, and graphite oxide is added, using magnetic agitation 4-6h to aoxidizing stone
Ink and phenolic resin are sufficiently mixed in dehydrated alcohol, and the container equipped with mixing liquid is put into 60-70 DEG C of water-bath and is steamed
Hair removal dehydrated alcohol, then dries 10h in drying box, and the material that drying obtains is put into high-temperature tubular sintering furnace,
N2Under the protection of atmosphere, 200 DEG C are risen to the heating rate of 10 DEG C/min, keeps the temperature 1h, is continuously heating to 600-700 DEG C of calcining
6h obtains the negative electrode active material of phenolic resin cladding graphite oxide after cooling.
Carrying out surface coated main function to graphite oxide is reduced irreversible on the active site for cover graphite surface
The generation of side reaction reduces graphite oxide specific surface area, inhibits the generation of SEI film, keeps apart graphite particle with electrolyte, prevents
Only solvent is inserted into altogether causes capacity to decline, and plays restriction and buffer function to the volume expansion of graphite, increases the stability of circulation.
Embodiment 1
The present embodiment provides a kind of preparation methods of high power environment-friendly type ferric phosphate lithium cell, include the following steps:
(1) preparation of anode material:
With FeCl2·4H2O、(NH4)2HPO4And LiOH3H2O is raw material, and the concentration of above-mentioned raw materials is 0.1M, first will
FeCl2·4H2O is dissolved in deionized water, and (NH is added later4)2HPO4, and be stirred continuously and occur until blackish green precipitates, centrifugation
Presoma Fe is obtained after removing solution3(PO4)2(H2O)8；Later by the LiOH3H of 0.1M2O is dissolved in deionized water, and is added
PH value of the citric acid of 0.1M to adjust solution is stirring evenly and then adding into presoma, continuing stirring makes presoma dissolution simultaneously to 2.5
It is uniformly mixed with solution；Mixed solution is transferred to autoclave again, is heated for 24 hours in 180 DEG C of temperature, in order to prevent Fe in solution2+
It is oxidized to Fe3+, filled with N in autoclave2；Then centrifuge washing precipitating and drying precipitated at 60 DEG C LiFePO is obtained for 24 hours4Just
Product；Finally containing 5%H again2Ar in calcine head product 10h, calcination temperature is selected as 500 DEG C, obtains flower pattern through calcining
LiFePO4Nanometer rods, as a positive electrode active material.
The LiFePO that will be prepared4Nanometer rods are taken out, with PVDF (Kynoar) and a certain amount of organic solvent N-
Binder is made in methyl pyrrolidone (NMP), puts into binder for the composition of conductive black and electrically conductive graphite as conductive agent
In, add LiFePO4Nanometer rods obtain anode material after mixing；Preferably, in anode material each component weight percent
Content are as follows: positive active material 90%, binder 5%, conductive agent 5%；
(2) preparation of positive plate:
Anode material is coated uniformly on the both side surface in positive pole aluminium foil collector other than tab, after vacuum drying, through pressing
After real, punching, positive plate is obtained, the surface density of positive plate is 250-280, compacted density 1.8-2.0.
(3) preparation of cathode material:
Using Hummers method, weighs to be put into after natural graphite is fully ground in the agate mortar and fill the concentrated sulfuric acid
It in beaker, is placed on magnetic stirring apparatus, at the uniform velocity stirs 1h at normal temperature, continue to stir 4-6h later in 60 DEG C of water-bath, so
Afterwards the solution being stirred is washed repeatedly with distilled water, place into and dry 12h in baking oven, the material for completing dry is put into high temperature
In pipe type sintering furnace, it is passed through N2200 DEG C are risen to the heating rate of 10 DEG C/min, 1h is kept the temperature, is continuously heating to 600 DEG C of constant temperature and forges
6h is burnt, obtains graphite oxide after cooling.
Phenolic resin is weighed according to 10% ratio of graphite oxide quality, is dissolved in dehydrated alcohol, and oxidation stone is added
Ink is sufficiently mixed in dehydrated alcohol using magnetic agitation 4h to graphite oxide and phenolic resin, and the appearance of mixing liquid will be housed
Device is put into evaporative removal dehydrated alcohol in 60 DEG C of water-bath, and 10h is then dried in drying box, and the material that drying obtains is put
Enter in high-temperature tubular sintering furnace, in N2Under the protection of atmosphere, 200 DEG C are risen to the heating rate of 10 DEG C/min, keeps the temperature 1h, is continued
600 DEG C of calcining 6h are warming up to, the negative electrode active material of phenolic resin cladding graphite oxide is obtained after cooling.
Binder is made with PVDF and organic solvent N-Methyl pyrrolidone, is put into using acetylene black as conductive agent viscous
It ties in agent, adds modified graphite oxide, after mixing, obtain cathode material；Preferably, in cathode material each component weight hundred
Divide content are as follows: negative electrode active material 88%, binder 6%, conductive agent 6%.
(4) preparation of negative electrode tab:
Cathode material is coated uniformly on the both side surface in cathode aluminum foil current collector other than tab, after being dried in vacuo 12h,
5MPa pressure pushes 2-3min, after being compacted, being punched, obtains negative electrode tab, the surface density of negative electrode tab is 100-130, compacted density
For 1.1-1.3.
(5) assembling of battery:
After positive plate is coated with membrane layer, outside is subject to negative electrode tab winding and forms cylindrical battery core, by cylindrical battery core
It is fitted into shell, top insulating trip and bottom insulation piece are installed in the both ends of cylindrical battery core, and installation power-off is anti-on positive pole ear
It is contacted after quick-fried component with nut cap, negative lug is contacted with shell, to interior of shell injecting power type electrolyte, is stood, encapsulation, system
Obtain battery.
Embodiment 2
The present embodiment provides a kind of preparation methods of high power environment-friendly type ferric phosphate lithium cell, include the following steps:
(1) preparation of anode material:
With FeCl2·4H2O、(NH4)2HPO4And LiOH3H2O is raw material, and the concentration of above-mentioned raw materials is 0.1M, first will
FeCl2·4H2O is dissolved in deionized water, and (NH is added later4)2HPO4, and be stirred continuously and occur until blackish green precipitates, centrifugation
Presoma Fe is obtained after removing solution3(PO4)2(H2O)8；Later by the LiOH3H of 0.1M2O is dissolved in deionized water, and is added
PH value of the citric acid of 0.1M to adjust solution is stirring evenly and then adding into presoma, continuing stirring makes presoma dissolution simultaneously to 3.5
It is uniformly mixed with solution；Mixed solution is transferred to autoclave again, is heated for 24 hours in 180 DEG C of temperature, in order to prevent Fe in solution2+
It is oxidized to Fe3+, filled with N in autoclave2；Then centrifuge washing precipitating and drying precipitated at 60 DEG C LiFePO is obtained for 24 hours4Just
Product；Finally containing 5%H again2Ar in calcine head product 10h, calcination temperature is selected as 550 DEG C, obtains flower pattern through calcining
LiFePO4Nanometer rods, as a positive electrode active material.
The LiFePO that will be prepared4Nanometer rods are taken out, with PVDF (Kynoar) and a certain amount of organic solvent N-
Binder is made in methyl pyrrolidone (NMP), using electrically conductive graphite as in conductive agent investment binder, adds LiFePO4It receives
Rice stick obtains anode material after mixing；Preferably, in anode material each component weight percentage are as follows: positive active material
86%, binder 7%, conductive agent 7%；
(2) preparation of positive plate:
Anode material is coated uniformly on the both side surface in positive pole aluminium foil collector other than tab, after vacuum drying, through pressing
After real, punching, positive plate is obtained, the surface density of positive plate is 250-280, compacted density 1.8-2.0.
(3) preparation of cathode material:
Using Hummers method, weighs to be put into after natural graphite is fully ground in the agate mortar and fill the concentrated sulfuric acid
It in beaker, is placed on magnetic stirring apparatus, at the uniform velocity stirs 1h at normal temperature, continue to stir 6h later in 60 DEG C of water-bath, then
The solution being stirred is washed repeatedly with distilled water, places into and dries 12h in baking oven, the material for completing dry is put into high temperature pipe
In formula sintering furnace, it is passed through N2200 DEG C are risen to the heating rate of 10 DEG C/min, 1h is kept the temperature, is continuously heating to 650 DEG C of calcining at constant temperature
6h obtains graphite oxide after cooling.
Phenolic resin is weighed according to 20% ratio of graphite oxide quality, is dissolved in dehydrated alcohol, and oxidation stone is added
Ink is sufficiently mixed in dehydrated alcohol using magnetic agitation 6h to graphite oxide and phenolic resin, and the appearance of mixing liquid will be housed
Device is put into evaporative removal dehydrated alcohol in 70 DEG C of water-bath, and 10h is then dried in drying box, and the material that drying obtains is put
Enter in high-temperature tubular sintering furnace, in N2Under the protection of atmosphere, 200 DEG C are risen to the heating rate of 10 DEG C/min, keeps the temperature 1h, is continued
650 DEG C of calcining 6h are warming up to, the negative electrode active material of phenolic resin cladding graphite oxide is obtained after cooling.
Binder is made with PVDF and organic solvent N-Methyl pyrrolidone, is put into using acetylene black as conductive agent viscous
It ties in agent, adds modified graphite oxide, after mixing, obtain cathode material；Preferably, in cathode material each component weight hundred
Divide content are as follows: negative electrode active material 90%, binder 5%, conductive agent 5%.
(4) preparation of negative electrode tab:
Cathode material is coated uniformly on the both side surface in cathode aluminum foil current collector other than tab, after being dried in vacuo 12h,
8MPa pressure pushes 2-3min, after being compacted, being punched, obtains negative electrode tab, the surface density of negative electrode tab is 100-130, compacted density
For 1.1-1.3.
(5) assembling of battery:
After positive plate is coated with membrane layer, outside is subject to negative electrode tab winding and forms cylindrical battery core, by cylindrical battery core
It is fitted into shell, top insulating trip and bottom insulation piece are installed in the both ends of cylindrical battery core, and installation power-off is anti-on positive pole ear
It is contacted after quick-fried component with nut cap, negative lug is contacted with shell, to interior of shell injecting power type electrolyte, is stood, encapsulation, system
Obtain battery.
Embodiment 3
The present embodiment provides a kind of preparation methods of high power environment-friendly type ferric phosphate lithium cell, include the following steps:
(1) preparation of anode material:
With FeCl2·4H2O、(NH4)2HPO4And LiOH3H2O is raw material, and the concentration of above-mentioned raw materials is 0.1M, first will
FeCl2·4H2O is dissolved in deionized water, and (NH is added later4)2HPO4, and be stirred continuously and occur until blackish green precipitates, centrifugation
Presoma Fe is obtained after removing solution3(PO4)2(H2O)8；Later by the LiOH3H of 0.1M2O is dissolved in deionized water, and is added
The citric acid of 0.1M is stirring evenly and then adding into presoma to adjust the pH value of solution to 3, continue stirring make presoma dissolve and with
Solution is uniformly mixed；Mixed solution is transferred to autoclave again, is heated for 24 hours in 180 DEG C of temperature, in order to prevent Fe in solution2+Oxygen
It is melted into Fe3+, filled with N in autoclave2；Then centrifuge washing precipitating and drying precipitated at 60 DEG C LiFePO is obtained for 24 hours4Primiparity
Object；Finally containing 5%H again2Ar in calcine head product 10h, calcination temperature is selected as 600 DEG C, obtains flower pattern LiFePO through calcining4
Nanometer rods, as a positive electrode active material.
The LiFePO that will be prepared4Nanometer rods are taken out, with PVDF (Kynoar) and a certain amount of organic solvent N-
Binder is made in methyl pyrrolidone (NMP), puts into binder using carbon fiber and the composition of carbon nanotube as conductive agent,
Add LiFePO4Nanometer rods obtain anode material after mixing；Preferably, in anode material each component weight percentage
Are as follows: positive active material 88%, binder 6%, conductive agent 6%；
(2) preparation of positive plate:
Anode material is coated uniformly on the both side surface in positive pole aluminium foil collector other than tab, after vacuum drying, through pressing
After real, punching, positive plate is obtained, the surface density of positive plate is 250-280, compacted density 1.8-2.0.
(3) preparation of cathode material:
Using Hummers method, weighs to be put into after natural graphite is fully ground in the agate mortar and fill the concentrated sulfuric acid
It in beaker, is placed on magnetic stirring apparatus, at the uniform velocity stirs 1h at normal temperature, continue to stir 6h later in 60 DEG C of water-bath, then
The solution being stirred is washed repeatedly with distilled water, places into and dries 12h in baking oven, the material for completing dry is put into high temperature pipe
In formula sintering furnace, it is passed through N2200 DEG C are risen to the heating rate of 10 DEG C/min, 1h is kept the temperature, is continuously heating to 700 DEG C of calcining at constant temperature
6h obtains graphite oxide after cooling.
Phenolic resin is weighed according to the ratio of the 10-20% of graphite oxide quality, is dissolved in dehydrated alcohol, and oxidation is added
Graphite is sufficiently mixed in dehydrated alcohol using magnetic agitation 6h to graphite oxide and phenolic resin, and mixing liquid will be housed
Container is put into evaporative removal dehydrated alcohol in 70 DEG C of water-bath, and 10h, the material that drying obtains then are dried in drying box
It is put into high-temperature tubular sintering furnace, in N2Under the protection of atmosphere, 200 DEG C are risen to the heating rate of 10 DEG C/min, keeps the temperature 1h, after
It is continuous to be warming up to 700 DEG C of calcining 6h, the negative electrode active material of phenolic resin cladding graphite oxide is obtained after cooling.
Binder is made with PVDF and organic solvent N-Methyl pyrrolidone, is put into using acetylene black as conductive agent viscous
It ties in agent, adds modified graphite oxide, after mixing, obtain cathode material；Preferably, in cathode material each component weight hundred
Divide content are as follows: negative electrode active material 86%, binder 7%, conductive agent 7%.
(4) preparation of negative electrode tab:
Cathode material is coated uniformly on the both side surface in cathode aluminum foil current collector other than tab, after being dried in vacuo 12h,
8MPa pressure pushes 2-3min, after being compacted, being punched, obtains negative electrode tab, the surface density of negative electrode tab is 100-130, compacted density
For 1.1-1.3.
(5) assembling of battery:
After positive plate is coated with membrane layer, outside is subject to negative electrode tab winding and forms cylindrical battery core, by cylindrical battery core
It is fitted into shell, top insulating trip and bottom insulation piece are installed in the both ends of cylindrical battery core, and installation power-off is anti-on positive pole ear
It is contacted after quick-fried component with nut cap, negative lug is contacted with shell, to interior of shell injecting power type electrolyte, is stood, encapsulation, system
Obtain battery.
Embodiment 4
The present embodiment provides a kind of preparation methods of high power environment-friendly type ferric phosphate lithium cell, include the following steps:
(1) preparation of anode material:
With FeCl2·4H2O、(NH4)2HPO4And LiOH3H2O is raw material, and the concentration of above-mentioned raw materials is 0.1M, first will
FeCl2·4H2O is dissolved in deionized water, and (NH is added later4)2HPO4, and be stirred continuously and occur until blackish green precipitates, centrifugation
Presoma Fe is obtained after removing solution3(PO4)2(H2O)8；Later by the LiOH3H of 0.1M2O is dissolved in deionized water, and is added
PH value of the citric acid of 0.1M to adjust solution is stirring evenly and then adding into presoma, continuing stirring makes presoma dissolution simultaneously to 3.2
It is uniformly mixed with solution；Mixed solution is transferred to autoclave again, is heated for 24 hours in 180 DEG C of temperature, in order to prevent Fe in solution2+
It is oxidized to Fe3+, filled with N in autoclave2；Then centrifuge washing precipitating and drying precipitated at 60 DEG C LiFePO is obtained for 24 hours4Just
Product；Finally containing 5%H again2Ar in calcine head product 10h, calcination temperature is selected as 650 DEG C, obtains flower pattern through calcining
LiFePO4Nanometer rods, as a positive electrode active material.
The LiFePO that will be prepared4Nanometer rods are taken out, with PVDF (Kynoar) and a certain amount of organic solvent N-
Binder is made in methyl pyrrolidone (NMP), using carbon nanotube as in conductive agent investment binder, adds LiFePO4It receives
Rice stick obtains anode material after mixing；Preferably, in anode material each component weight percentage are as follows: positive active material
80%, binder 10%, conductive agent 10%；
(2) preparation of positive plate:
Anode material is coated uniformly on the both side surface in positive pole aluminium foil collector other than tab, after vacuum drying, through pressing
After real, punching, positive plate is obtained, the surface density of positive plate is 250-280, compacted density 1.8-2.0.
(3) preparation of cathode material:
Using Hummers method, weighs to be put into after natural graphite is fully ground in the agate mortar and fill the concentrated sulfuric acid
It in beaker, is placed on magnetic stirring apparatus, at the uniform velocity stirs 1h at normal temperature, continue to stir 6h later in 60 DEG C of water-bath, then
The solution being stirred is washed repeatedly with distilled water, places into and dries 12h in baking oven, the material for completing dry is put into high temperature pipe
In formula sintering furnace, it is passed through N2200 DEG C are risen to the heating rate of 10 DEG C/min, 1h is kept the temperature, is continuously heating to 700 DEG C of calcining at constant temperature
6h obtains graphite oxide after cooling.
Phenolic resin is weighed according to the ratio of the 10-20% of graphite oxide quality, is dissolved in dehydrated alcohol, and oxidation is added
Graphite is sufficiently mixed in dehydrated alcohol using magnetic agitation 4-6h to graphite oxide and phenolic resin, and mixing liquid will be housed
Container be put into evaporative removal dehydrated alcohol in 70 DEG C of water-bath, 10h, the material that drying obtains then are dried in drying box
Material is put into high-temperature tubular sintering furnace, in N2Under the protections of atmosphere, 200 DEG C are risen to the heating rate of 10 DEG C/min, keeps the temperature 1h,
700 DEG C of calcining 6h are continuously heating to, the negative electrode active material of phenolic resin cladding graphite oxide is obtained after cooling.
Binder is made with PVDF and organic solvent N-Methyl pyrrolidone, is put into using acetylene black as conductive agent viscous
It ties in agent, adds modified graphite oxide, after mixing, obtain cathode material；Preferably, in cathode material each component weight hundred
Divide content are as follows: negative electrode active material 80%, binder 10%, conductive agent 10%.
(4) preparation of negative electrode tab:
Cathode material is coated uniformly on the both side surface in cathode aluminum foil current collector other than tab, after being dried in vacuo 12h,
8MPa pressure pushes 2-3min, after being compacted, being punched, obtains negative electrode tab, the surface density of negative electrode tab is 100-130, compacted density
For 1.1-1.3.
(5) assembling of battery:
After positive plate is coated with membrane layer, outside is subject to negative electrode tab winding and forms cylindrical battery core, by cylindrical battery core
It is fitted into shell, top insulating trip and bottom insulation piece are installed in the both ends of cylindrical battery core, and installation power-off is anti-on positive pole ear
It is contacted after quick-fried component with nut cap, negative lug is contacted with shell, to interior of shell injecting power type electrolyte, is stood, encapsulation, system
Obtain battery.
Embodiment 5
The present embodiment provides a kind of preparation method of high power environment-friendly type ferric phosphate lithium cell, step and parameter and implementation
Example 4 is similar, unique difference be in:
In the present embodiment, the weight percentage of each component in anode material are as follows: positive active material 83%, binder 7%,
Conductive agent 10%；The weight percentage of each component in cathode material are as follows: negative electrode active material 85%, binder 7%, conductive agent
8%.
Comparative example
As a comparison case with existing ferric phosphate lithium cell.
Performance Evaluation is carried out to the battery of above-described embodiment 1-5 and comparative example in accordance with the following methods.
1. gravimetric energy density is tested
Under 25 DEG C ± 5 DEG C of environment temperature, above-mentioned single battery is charged to when voltage reaches 3.6V with 0.5C and turns perseverance
Pressure charging, charge when charging current drops to 0.6A terminates, and stopping is put when with 0.5C constant current discharge to final voltage 2.5V
Electricity is calculated the gravimetric energy density of single battery by formula (1).
Es=E/m ... ... ... ... ... ... (1)
In formula: Es-gravimetric energy density, Wh/kg；
E-is by the single battery discharge energy that directly reads on discharge equipment, Wh；
M-single battery weight, kg.
2. high current cycle performance and temperature rise
Under 25 DEG C ± 5 DEG C of environment temperature, above-mentioned single battery is charged to when voltage reaches 3.6V with 0.5C and turns perseverance
Pressure charging, charging when charging current drops to 0.6A terminates, after shelving 0.5h, with 1C and 2C constant current discharge to final voltage
Stop electric discharge when 2V；It is shelved at room temperature after electric discharge and is completely cooled down to room temperature to single battery, count Cheng Yici charge and discharge
Cyclic process.Repeat charge and discharge cycles, stops test after amounting to circulation 50 times, test residual capacity and temperature change.
Test result is as shown in table 1:
1 embodiment of table and comparative example detection data compare
By detection data it is found that compared to comparative example, the gravimetric energy density of embodiment 1-5 improves 22% or so,
The material and structure for illustrating the ferric phosphate lithium cell that the present invention uses are conducive to the energy density for promoting battery；By repeatedly filling
Discharge cycles, embodiment 1-5 capacity residue with higher and lower temperature rise illustrate through aluminum foil current collector, power-type electricity
The synergy of liquid etc. is solved, the present invention has more excellent charge/discharge capacity and service life compared to comparative example, more suitable for
Long-term cycle operation.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without
It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be within the scope of protection determined by the claims.
Claims (10)
1. a kind of high power environment-friendly type ferric phosphate lithium cell includes cylindrical shell, which is characterized in that cylindrical shell
Bottom is equipped with bottom insulation piece, and the top of cylindrical shell is equipped with the nut cap for constituting positive terminal, nut cap and cylindrical shell top
Between be distributed with sealing ring, safety valve and top insulating trip are disposed in the axial direction of cylindrical shell below nut cap；
Cylindrical housing interior constitutes battery accommodating space, and the center of battery accommodating space is equipped with the positive plate for being curled into tubular, just
Pole piece is coated with positive electrode active material layer, conducting agent layer and adhesive layer, and positive electrode active material layer is by lithium iron phosphate nano
Bar construction is equipped with negative electrode tab in positive plate interval to constitute cylindrical battery core, and the bottom of cylindrical battery core is equipped with bottom insulation
Piece is coated with negative electrode active material layer, conducting agent layer and adhesive layer on the surface of negative electrode tab, and negative electrode active material layer is by through phenol
Urea formaldehyde cladding graphite oxide constitute, be equipped between positive plate and negative electrode tab, between negative electrode tab and cylindrical shell every
Positive pole ear is distributed between cylindrical battery core and nut cap in film layer, and the negative lug for stretching out shape is equipped in the tail portion of negative electrode tab,
It is filled with power-type electrolyte between positive plate and negative electrode tab, power-off proof assembl is distributed on positive pole ear, powers off explosion-proof
Component is screw thread solenoid valve, and when inside battery air pressure is excessive, the elastic slice in screw thread solenoid valve is opened, so that in battery
The high pressure gas in portion is discharged；After the air pressure decline of inside battery, elastic slice resets under the action of spring restoring force.
2. high power environment-friendly type ferric phosphate lithium cell as described in claim 1, which is characterized in that safety valve includes valve body, close
Sealing ball and thimble are provided with arcwall face, sealing are provided in bleed passage through there is bleed passage in valve body in bleed passage
Glueballs, sealing glueballs are close to arcwall face with closed valve, and thimble is set to the top of sealing glueballs, and one end of thimble is puncture portion
And offset with sealing glueballs, the other end of thimble is fixed part and the inner sidewall for being fixed on bleed passage.
3. high power environment-friendly type ferric phosphate lithium cell as claimed in claim 2, which is characterized in that bleed passage includes having the
The upper cylindrical channel of Radius and lower cylindrical channel with the second radius, wherein upper cylindrical channel and lower cylinder
It is connect between channel by arc-shaped changeover portion compatible with sealing glueballs.
4. high power environment-friendly type ferric phosphate lithium cell as described in claim 1, which is characterized in that positive active material is phosphoric acid
Iron lithium nanometer rods, negative electrode active material are the graphite oxide coated through phenolic resin, constitute three layers of membrane layer PP, PE and PP
Composite diaphragm, power-type electrolyte are the mixed solutions of lithium salts, functional additive and organic solvent.
5. a kind of preparation method of high power environment-friendly type ferric phosphate lithium cell as described in claim 1, which is characterized in that including
Following steps:
(1) preparation of anode material: with FeCl2·4H2O、(NH4)2HPO4And LiOH3H2O is raw material, is prepared by hydro-thermal method
Obtain flower pattern LiFePO4Bonding is made as a positive electrode active material, with PVDF and organic solvent N-Methyl pyrrolidone in nanometer rods
Agent puts into one or more of conductive agents in conductive black, electrically conductive graphite, carbon fiber, carbon nanotube in binder, then
LiFePO is added4Nanometer rods obtain anode material after mixing；
(2) anode material the preparation of positive plate: is coated uniformly on the both side surface in positive pole aluminium foil collector other than tab, vacuum
After drying, after being compacted, being punched, positive plate is obtained；
(3) preparation of cathode material: using the concentrated sulfuric acid as oxidant, graphite oxide is prepared using Hummers method, is coated with phenolic resin
Mode graphite oxide is modified, to obtain negative electrode active material, with PVDF and organic solvent N-Methyl pyrrolidone system
It at binder, is put into acetylene black as conductive agent in binder, adds modified graphite oxide, after mixing, obtained
Cathode material；
(4) cathode material the preparation of negative electrode tab: is coated uniformly on the both side surface in cathode aluminum foil current collector other than tab, vacuum
After drying, after being compacted, being punched, negative electrode tab is obtained；
(5) assembling of battery: after positive plate is coated with membrane layer, outside is subject to negative electrode tab winding and forms cylindrical battery core, will
Cylindrical battery core is fitted into shell, and top insulating trip and bottom insulation piece is installed at the both ends of cylindrical battery core, on positive pole ear
It is contacted after installation power-off proof assembl with nut cap, negative lug is contacted with shell, quiet to interior of shell injecting power type electrolyte
It sets, encapsulate, battery is made.
6. preparation method as claimed in claim 5, which is characterized in that LiFePO is prepared according to the following steps4Nanometer rods: first
By FeCl2·4H2O is dissolved in deionized water, and (NH is added later4)2HPO4, and be stirred continuously and occur until blackish green precipitates, from
The heart obtains presoma Fe after removing solution3(PO4)2(H2O)8；Later by LiOH3H2O is dissolved in deionized water, and citric acid is added
PH value to adjust solution is stirring evenly and then adding into presoma, continuing stirring makes presoma dissolve and mix with solution to 2.5-3.5
It closes uniform；Mixed solution is transferred to filled with N again2Autoclave, 180 DEG C temperature heating for 24 hours, then centrifuge washing precipitating simultaneously
It is drying precipitated at 60 DEG C to obtain LiFePO for 24 hours4Head product；Finally containing 5%H again2Ar in calcine head product 10h, calcining temperature
Degree is selected as 500-650 DEG C, finally obtains LiFePO4Nanometer rods.
7. preparation method as claimed in claim 5, which is characterized in that graphite oxide is prepared according to the following steps: weighing day
Right graphite is put into the beaker for filling the concentrated sulfuric acid after being fully ground in the agate mortar, is placed on magnetic stirring apparatus, normal
1h is at the uniform velocity stirred under temperature, continue in 60 DEG C of water-bath later stir 4-6h, then by the solution being stirred with distilled water repeatedly
Washing, places into and dries 12h in baking oven, and the material for completing dry is put into high-temperature tubular sintering furnace, N is passed through2With 10 DEG C/
The heating rate of min rises to 200 DEG C, keeps the temperature 1h, is continuously heating to 600-700 DEG C of calcining at constant temperature 6h, and oxidation stone is obtained after cooling
Ink.
8. preparation method as claimed in claim 5, which is characterized in that the negative electrode active material of phenolic resin cladding graphite oxide
The preparation method comprises the following steps: weigh phenolic resin according to the ratio of the 10-20% of graphite oxide quality, be dissolved in dehydrated alcohol, and add
Enter graphite oxide, is sufficiently mixed in dehydrated alcohol using magnetic agitation 4-6h to graphite oxide and phenolic resin, it will be equipped with mixed
The container for closing liquid is put into evaporative removal dehydrated alcohol in 60-70 DEG C of water-bath, 10h is then dried in drying box, through drying
Dry obtained material is put into high-temperature tubular sintering furnace, in N2Under the protection of atmosphere, 200 are risen to the heating rate of 10 DEG C/min
DEG C, 1h is kept the temperature, 600-700 DEG C of calcining 6h is continuously heating to, the negative electrode active of phenolic resin cladding graphite oxide is obtained after cooling
Substance.
9. preparation method as claimed in claim 5, which is characterized in that the weight percentage of each component in anode material are as follows: just
Pole active material 80-90%, binder 5-10%, conductive agent 5-10%；The weight percentage of each component in cathode material are as follows: negative
Pole active material 80-90%, binder 5-10%, conductive agent 5-10%.
10. preparation method as claimed in claim 5, which is characterized in that the surface density of positive plate is 250-280, compacted density
For 1.8-2.0；The surface density of negative electrode tab is 100-130, compacted density 1.1-1.3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910119360.6A CN109786618A (en) | 2019-02-18 | 2019-02-18 | A kind of high power environment-friendly type ferric phosphate lithium cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910119360.6A CN109786618A (en) | 2019-02-18 | 2019-02-18 | A kind of high power environment-friendly type ferric phosphate lithium cell and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109786618A true CN109786618A (en) | 2019-05-21 |
Family
ID=66503325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910119360.6A Pending CN109786618A (en) | 2019-02-18 | 2019-02-18 | A kind of high power environment-friendly type ferric phosphate lithium cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109786618A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252693A (en) * | 2019-06-18 | 2019-09-20 | 芜湖天弋能源科技有限公司 | A kind of quick minimizing technology of electrodes of lithium-ion batteries single side slurry |
| CN111816881A (en) * | 2019-08-28 | 2020-10-23 | 中南大学 | Rambutan-like shell-shaped 3D lithium-philic composite current collector, lithium metal negative electrode, and preparation and application thereof |
| CN113906625A (en) * | 2021-03-22 | 2022-01-07 | 宁德新能源科技有限公司 | Battery cell and power utilization device |
| CN114361569A (en) * | 2022-01-06 | 2022-04-15 | 广州小鹏汽车科技有限公司 | Cylindrical battery, preparation method thereof and vehicle |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201936955U (en) * | 2011-01-13 | 2011-08-17 | 苏州能斯特新能源有限公司 | Cylindrical lithium battery |
| CN106602133A (en) * | 2016-12-28 | 2017-04-26 | 中国电子科技集团公司第十八研究所 | Lithium iron phosphate battery with high specific property and preparation method thereof |
-
2019
- 2019-02-18 CN CN201910119360.6A patent/CN109786618A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201936955U (en) * | 2011-01-13 | 2011-08-17 | 苏州能斯特新能源有限公司 | Cylindrical lithium battery |
| CN106602133A (en) * | 2016-12-28 | 2017-04-26 | 中国电子科技集团公司第十八研究所 | Lithium iron phosphate battery with high specific property and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252693A (en) * | 2019-06-18 | 2019-09-20 | 芜湖天弋能源科技有限公司 | A kind of quick minimizing technology of electrodes of lithium-ion batteries single side slurry |
| CN111816881A (en) * | 2019-08-28 | 2020-10-23 | 中南大学 | Rambutan-like shell-shaped 3D lithium-philic composite current collector, lithium metal negative electrode, and preparation and application thereof |
| CN113906625A (en) * | 2021-03-22 | 2022-01-07 | 宁德新能源科技有限公司 | Battery cell and power utilization device |
| WO2022198411A1 (en) * | 2021-03-22 | 2022-09-29 | 宁德新能源科技有限公司 | Battery cell and power consumption apparatus |
| CN114361569A (en) * | 2022-01-06 | 2022-04-15 | 广州小鹏汽车科技有限公司 | Cylindrical battery, preparation method thereof and vehicle |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109786618A (en) | A kind of high power environment-friendly type ferric phosphate lithium cell and preparation method thereof | |
| CN101081696B (en) | Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof | |
| CN101826634B (en) | Lithium ion battery and manufacturing method thereof | |
| CN102637866B (en) | Method for preparing lithium ion battery anode material with concentration gradient | |
| CN104934579B (en) | A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material | |
| CN108232156B (en) | Silicon-carbon composite cathode for solid-state battery and preparation method thereof | |
| CN201153140Y (en) | High-safety polymer battery positive pole | |
| CN102544481A (en) | Lithium ion battery and cathode material thereof | |
| CN103579590A (en) | Preparation method for coating anode material of lithium battery | |
| CN105552324A (en) | Preparation method for lithium iron phosphate coated lithium nickel cobalt manganese composite material | |
| CN106654169A (en) | Positive electrode plate of lithium ion battery and preparation method for positive electrode plate | |
| CN103280601B (en) | Method for manufacturing lithium-sulfur battery | |
| CN103474625A (en) | Coating method for core-shell novel positive electrode material for lithium ion battery | |
| CN102244233B (en) | Method for preparing composite cathode material of graphene-like doped-cladded lithium titanate | |
| CN103474723A (en) | Lithium-air battery and preparation method thereof | |
| CN115566255B (en) | Secondary battery and electric equipment | |
| CN107935049A (en) | A kind of lithium ion battery negative material Bi2Mn4O10Preparation and its application | |
| CN102185163B (en) | Method for preparing inorganic aqueous solution lithium ion battery system by using monocrystal LiMnO (lithium manganese oxide) nanowire | |
| CN108807912A (en) | A kind of C@SnOx(x=0,1,2)The preparation and application of the mesoporous shape hollow nano spherical structures of@C | |
| CN111313010A (en) | Preparation method of high-capacity lithium ion battery anode material lithium iron phosphate | |
| CN111180704A (en) | Sodium-ion battery positive electrode material and preparation method and application thereof | |
| CN110459768A (en) | A kind of octahedral structure iron phosphide/carbon composite and the preparation method and application thereof | |
| CN102881882B (en) | Preparation method and application of thin-wall capsule-shaped lithium titanate electrode material | |
| CN110364681A (en) | A kind of based lithium-ion battery positive plate of the high security of triple protection | |
| CN105958027A (en) | Manganese-based composite positive electrode material and preparation method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190521 |
|
| RJ01 | Rejection of invention patent application after publication |