CN102820471A - High-safety lithium ion battery cathode material and its preparation method - Google Patents
High-safety lithium ion battery cathode material and its preparation method Download PDFInfo
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- CN102820471A CN102820471A CN2011104076171A CN201110407617A CN102820471A CN 102820471 A CN102820471 A CN 102820471A CN 2011104076171 A CN2011104076171 A CN 2011104076171A CN 201110407617 A CN201110407617 A CN 201110407617A CN 102820471 A CN102820471 A CN 102820471A
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- lialo
- graphite
- lithium ion
- afterwards
- colloidal sol
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 36
- 239000010406 cathode material Substances 0.000 title abstract 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 57
- 239000010439 graphite Substances 0.000 claims abstract description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000010453 quartz Substances 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 17
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 229910010093 LiAlO Inorganic materials 0.000 claims description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000003708 ampul Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 30
- 239000007773 negative electrode material Substances 0.000 claims description 29
- 239000008187 granular material Substances 0.000 claims description 26
- 239000002270 dispersing agent Substances 0.000 claims description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- -1 carbon nano tube compound Chemical class 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000009423 ventilation Methods 0.000 claims description 12
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 10
- 150000003863 ammonium salts Chemical class 0.000 claims description 10
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 3
- 229910010092 LiAlO2 Inorganic materials 0.000 abstract 5
- 239000000843 powder Substances 0.000 abstract 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract 1
- 229910001679 gibbsite Inorganic materials 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 18
- 229910052744 lithium Inorganic materials 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- 229940068984 polyvinyl alcohol Drugs 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 241000736199 Paeonia Species 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 210000000352 storage cell Anatomy 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of lithium ion batteries, and concretely discloses a high-safety lithium ion battery cathode material and its preparation method. The preparation method of the high-safety lithium ion battery cathode material comprises the following steps: reacting an Al(OH)3 sol with NaOH and LiOH at 40-90DEG C to prepare LiAlO2, mixing graphite with the LiAlO2, adjusting the pH value, heating to 500-800DEG C to remove organic compounds and water, and grinding to obtain graphite/LiAlO2 composite powder; and putting the graphite/LiAlO2 composite powder under an iron catalyst in a quartz tube to prepare an LiAlO2/carbon nanotube composite material, and ball-milling to obtain the high-safety lithium ion battery cathode material. The high-safety lithium ion battery cathode material provided by the invention has an excellent safety performance, and is especially suitable for large capacity and high rate lithium ion batteries.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of high security lithium ion cell negative electrode material and preparation method thereof.
Background technology
Lithium ion battery is a kind of novel energy storage cell that grew up in recent years; With its have extended cycle life, working voltage platform is steady, advantage such as cheap and pollution-free receives people's attention, has been widely used in fields such as electric automobile, wind energy energy storage, mobile power station at present.
One of bottleneck of restriction lithium ion battery development is the security performance problem of battery at present.The measure that is used to improve the security performance of lithium ion battery at present mainly is divided into two kinds, promptly outside measure and internal measure.Outside measure mainly is to add battery safety valve through the sealing part at lithium ion battery to achieve the goal, and internal measure mainly is to realize through the internal structure design and use material that changes lithium ion battery.The researcher is carrying out many researchs aspect the employing internal measure raising lithium ion battery security energy at present; Such as adding flame-retardant electrolyte, use ceramic diaphragm, make negative material excessive etc., but yet there are no by changing the negative material surface texture to improve the research report that lithium ion battery security can the aspect.Owing to one of reason that causes the lithium ion battery potential safety hazard is exactly owing to lithium is analysed on negative material surface in the lithium ion battery charge and discharge process; Be that lithium ion is when going to negative pole and prepare embedding; Because of some reason (such as big, the big multiplying power discharging of positive maximum dose ratio, low temperature etc.) when causing the space that holds lithium ion not enough; Lithium ion just forms dendrite at the surface sediment of negative pole, thereby puncturing barrier film causes the lithium ion battery short circuit, and the security performance of lithium ion battery is descended; Therefore, effectively solving dendrite, to puncture the barrier film problem extremely important to the security performance that improves lithium ion battery.
Summary of the invention
The object of the present invention is to provide a kind of high security lithium ion cell negative electrode material.
The present invention also aims to provide a kind of preparation method of high security lithium ion cell negative electrode material.
In order to realize above purpose, the technical scheme that the present invention adopted is: a kind of high security lithium ion cell negative electrode material, process through following steps:
(1) preparation Al (OH)
3Colloidal sol
With AlCl
3At 200～300 ℃ of pyrogenically prepared aluminium chlorides, afterwards aluminium chloride is used deionized water dissolving, filter, obtain filtrating, in said filtrating, add organic dispersing agent solution and ammonium salt, under 40～90 ℃ of temperature, react 6～48h afterwards, make Al (OH)
3Colloidal sol;
(2) preparation graphite/LiAlO
2Composite granule
The Al (OH) that step (1) is made
3Colloidal sol mixes with NaOH, LiOH, under 40～90 ℃ of temperature, reacts 6～48h, makes LiAlO
2, afterwards graphite is added said LiAlO
2In and be uniformly dispersed; Get dispersed system A, the pH value with said dispersed system A transfers to 7～9 then, gets even colloidal sol compound system; Heat said even colloidal sol compound system down at 500～800 ℃ afterwards; Steam the organic dispersing agent and the moisture that remove in the said even colloidal sol compound system, get solids, grind said solids afterwards and obtain graphite/LiAlO
2Composite granule;
(3) preparation graphite/LiAlO
2/ carbon nano tube compound material
Graphite/LiAlO that step (2) is made
2Composite granule, iron catalyst are put into quartz ampoule, and heated quarty tube and in quartz ampoule, feed nitrogen is closed nitrogen when being warming up to 800～1000 ℃ then; Logical hydrogen in said quartz ampoule, duration of ventilation is 1～2 hour, temperature remains 800～1000 ℃; Close hydrogen afterwards, logical acetylene or methane gas in said quartz ampoule, duration of ventilation is 1～2 hour; Temperature remains 800～1000 ℃; Close acetylene or methane gas afterwards, in said quartz ampoule, feed nitrogen to said quartz ampoule again and be cooled to room temperature, make graphite/LiAlO
2/ carbon nano tube compound material, said graphite/LiAlO
2/ carbon nano tube compound material obtains the high security lithium ion cell negative electrode material again through ball milling.
Further, the concentration of said filtrating is 0.1～1.0mol/L.
Said organic dispersing agent solution is the polyethylene glycol aqueous solution or polyvinyl alcohol water solution, and the mass percent concentration of said organic dispersing agent solution is 20～50%.Wherein, organic dispersing agent solution is to add in the aqueous solvent formulated by organic dispersing agent through ultrasonic dispersion.
Said ammonium salt is ammonium chloride or ammonium sulfate.
In the step (1), AlCl
3Quality, organic dispersing agent solution in the ratio of quality of quality and ammonium salt of contained organic dispersing agent be: AlCl
3Quality: the quality of contained organic dispersing agent in the organic dispersing agent solution: the quality of ammonium salt=1: (0.1～0.3): (0.2～0.5).
Al (OH) in the step (2)
3Al in the colloidal sol (OH)
3, with the mol ratio of NaOH, LiOH be: Al (OH)
3: NaOH: LiOH=1: (1～1.5): (1～1.5).
Graphite and LiAlO in the step (2)
2Mass ratio be: graphite: LiAlO
2=1: (0.01～0.1).
Said graphite is Delanium or carbonaceous mesophase spherules.
Graphite/LiAlO in the step (3)
2The mass ratio of composite granule and iron catalyst is: graphite/LiAlO
2Composite granule: iron catalyst=1: (0.01～1).
A kind of preparation method of high security lithium ion cell negative electrode material may further comprise the steps:
(1) preparation Al (OH)
3Colloidal sol
With AlCl
3At 200～300 ℃ of pyrogenically prepared aluminium chlorides, afterwards aluminium chloride is used deionized water dissolving, filter, obtain filtrating, in said filtrating, add organic dispersing agent solution and ammonium salt, under 40～90 ℃ of temperature, react 6～48h afterwards, make Al (OH)
3Colloidal sol;
(2) preparation graphite/LiAlO
2Composite granule
The Al (OH) that step (1) is made
3Colloidal sol mixes with NaOH, LiOH, under 40～90 ℃ of temperature, reacts 6～48h, makes LiAlO
2, afterwards graphite is added said LiAlO
2In and be uniformly dispersed; Get dispersed system A, the pH value with said dispersed system A transfers to 7～9 then, gets even colloidal sol compound system; Heat said even colloidal sol compound system down at 500～800 ℃ afterwards; Steam the organic dispersing agent and the moisture that remove in the said even colloidal sol compound system, get solids, grind said solids afterwards and obtain graphite/LiAlO
2Composite granule;
(3) preparation graphite/LiAlO
2/ carbon nano tube compound material
Graphite/LiAlO that step (2) is made
2Composite granule, iron catalyst are put into quartz ampoule, and heated quarty tube and in quartz ampoule, feed nitrogen is closed nitrogen when being warming up to 800～1000 ℃ then; Logical hydrogen in said quartz ampoule, duration of ventilation is 1～2 hour, temperature remains 800～1000 ℃; Close hydrogen afterwards, logical acetylene or methane gas in said quartz ampoule, duration of ventilation is 1～2 hour; Temperature remains 800～1000 ℃; Close acetylene or methane gas afterwards, in said quartz ampoule, feed nitrogen to said quartz ampoule again and be cooled to room temperature, make graphite/LiAlO
2/ carbon nano tube compound material, said graphite/LiAlO
2/ carbon nano tube compound material obtains the high security lithium ion cell negative electrode material again through ball milling.
High security lithium ion cell negative electrode material provided by the invention surface has coated one deck LiAlO
2Lithium salt compound; The dendrite on negative material surface and effective isolation of barrier film have been realized; Reduce lithium ion battery and in improper use, produced the generation of analysing security incidents such as the lithium ion battery that lithium causes catches fire, blast, burning, improved the security performance of lithium ion battery.
The high security lithium ion cell negative electrode material that the present invention makes through the negative material surface modification had both kept graphite as the characteristic that negative material had, and had utilized lithium ion battery LiAlO in charge and discharge process again
2The characteristic of ionic conductivity; Improved the conduction velocity of lithium ion battery; Reduce lithium ion battery and analysed the probability that dendrite that lithium produces punctures barrier film, also utilized the electron conduction characteristic of CNT simultaneously, improved the conductivity of high security lithium ion cell negative electrode material.High security lithium ion cell negative electrode material provided by the invention had both utilized LiAlO
2Ionic conductivity in the lithium ion battery charge and discharge process; Utilized the electron conduction of CNT again; Thereby the transmission rate of raising lithium ion battery and the conduction of electronics have been played positive role, reduced simultaneously and analysed the danger that lithium produces, therefore; High security lithium ion cell negative electrode material provided by the invention has the security performance excellent characteristic, is particularly useful for big capacity high multiplying power lithium ion battery.
Description of drawings
Fig. 1 is the SEM figure of the lithium ion battery negative material of embodiment 1 preparation;
Fig. 2 overcharges back pole piece picture for the battery and the normal battery of embodiment 1 preparation.
Embodiment
Embodiment 1
The high security lithium ion cell negative electrode material that present embodiment provides is processed through following steps:
(1) preparation Al (OH)
3Colloidal sol
With AlCl
3At 300 ℃ of pyrogenically prepared aluminium chlorides; Afterwards aluminium chloride is used deionized water dissolving, filter, obtain filtrating; The concentration of filtrating is 0.1mol/L; The adding mass percent concentration is 50% polyglycol solution in filtrating, and then in filtrating, adds ammonium chloride, makes Al (OH) 90 ℃ of reactions then
3Colloidal sol; AlCl wherein
3Quality: the quality of polyethylene glycol in the polyglycol solution: the quality of ammonium chloride=1: 0.3: 0.2;
(2) preparation graphite/LiAlO
2Composite granule
The Al (OH) that step (1) is made
3Colloidal sol mixes with NaOH, LiOH, Al (OH)
3Al in the colloidal sol (OH)
3, with the mol ratio of NaOH, LiOH be: Al (OH)
3: NaOH: LiOH=1: 1: 1.5; Make LiAlO 40 ℃ of reactions then
2, afterwards Delanium is added LiAlO
2In and be uniformly dispersed, dispersed system A, wherein Delanium and LiAlO
2Mass ratio be: Delanium: LiAlO
2=1: 0.1, the pH value with dispersed system A transfers to 9 then, gets even colloidal sol compound system; Afterwards at 500 ℃ of following homogeneous heating colloidal sol compound systems; Steam the organic compound and the moisture that remove in the even colloidal sol compound system, get solids, the abrasive solid thing obtains graphite/LiAlO afterwards
2Composite granule;
(3) preparation graphite/LiAlO
2/ carbon nano tube compound material
Graphite/LiAlO that step (2) is made
2Composite granule, iron catalyst are put into quartz ampoule, graphite/LiAlO
2The mass ratio of composite granule and iron catalyst is: graphite/LiAlO
2Composite granule: iron catalyst=1: 1, heated quarty tube and in quartz ampoule, feed nitrogen is closed nitrogen when being warming up to 1000 ℃ then, logical hydrogen in quartz ampoule; Duration of ventilation is 1 hour, and temperature remains 1000 ℃, closes hydrogen afterwards; Ventilating methane gas in quartz ampoule, duration of ventilation are 2 hours, and temperature remains 1000 ℃; Close methane gas afterwards, in quartz ampoule, feed nitrogen to quartz ampoule again and be cooled to room temperature, make graphite/LiAlO
2/ carbon nano tube compound material again through ball milling, obtains the high security lithium ion cell negative electrode material.
Embodiment 2
The high security lithium ion cell negative electrode material that present embodiment provides is processed through following steps:
(1) preparation Al (OH)
3Colloidal sol
With AlCl
3At 200 ℃ of pyrogenically prepared aluminium chlorides; Afterwards aluminium chloride is used deionized water dissolving, filter, obtain filtrating; The concentration of filtrating is 1.0mol/L; The adding mass percent concentration is 20% poly-vinyl alcohol solution in filtrating, and then in filtrating, adds ammonium sulfate, makes Al (OH) 40 ℃ of reactions then
3Colloidal sol; AlCl wherein
3Quality: the quality of polyvinyl alcohol in the poly-vinyl alcohol solution: the quality of ammonium sulfate=1: 0.1: 0.5;
(2) preparation graphite/LiAlO
2Composite granule
The Al (OH) that step (1) is made
3Colloidal sol mixes with NaOH, LiOH, Al (OH)
3Al in the colloidal sol (OH)
3, with the mol ratio of NaOH, LiOH be: Al (OH)
3: NaOH: LiOH=1: 1.5: 1; Make LiAlO 90 ℃ of reactions then
2, afterwards carbonaceous mesophase spherules is added LiAlO
2In and be uniformly dispersed, dispersed system A, wherein carbonaceous mesophase spherules and LiAlO
2Mass ratio be: carbonaceous mesophase spherules: LiAlO
2=1: 0.01, the pH value with dispersed system A transfers to 7 then, gets even colloidal sol compound system; Afterwards at 800 ℃ of following homogeneous heating colloidal sol compound systems; Steam the organic compound and the moisture that remove in the even colloidal sol compound system, get solids, the abrasive solid thing obtains graphite/LiAlO afterwards
2Composite granule;
(3) preparation graphite/LiAlO
2/ carbon nano tube compound material
Graphite/LiAlO that step (2) is made
2Composite granule, iron catalyst are put into quartz ampoule, graphite/LiAlO
2The mass ratio of composite granule and iron catalyst is: graphite/LiAlO
2Composite granule: iron catalyst=1: 0.01, heated quarty tube and in quartz ampoule, feed nitrogen is closed nitrogen when being warming up to 800 ℃ then, logical hydrogen in quartz ampoule; Duration of ventilation is 2 hours, and temperature remains 800 ℃, closes hydrogen afterwards; Logical acetylene gas in quartz ampoule, duration of ventilation is 1 hour, temperature remains 800 ℃; Close acetylene gas afterwards, in quartz ampoule, feed nitrogen to quartz ampoule again and be cooled to room temperature, make graphite/LiAlO
2/ carbon nano tube compound material again through ball milling, obtains the high security lithium ion cell negative electrode material.
Experimental example:
Graphite/LiAlO with embodiment 1 preparation
2/ CNT is a negative material, and LiFePO4 is a positive electrode, uses 1.0mol/L LiPF
6/ EC+DEC (V
EC: V
DEC=1: 1) (EC:ethylene carbonate, ethylene carbonate; DEC:diethyl carbonate; Diethyl carbonate) makes electrolyte; U.S. Celgard 2300 is a barrier film, and the lithium ion battery of preparing 40AH is (battery a), afterwards to its battery test (because battery overcharge that overcharges; Lithium ion in the positive electrode can cause negative terminal surface to analyse lithium in the negative terminal surface run-up and cause the dangerous of battery), separate the lithium situation of analysing that its battery is observed its negative material surface of digging afterwards.And under equal conditions to the test of overcharging of the battery (battery b) of normal negative material preparation; Separate the lithium situation of analysing that its battery is observed its negative material surface of digging afterwards: the result shows that the negative material surface color of the battery (a) of the inventive method preparation presents golden yellow; Promptly do not have lithium metal and separate out, and control cell (b) negative material surface color presents peony even black explanation surface has more lithium ion to separate out.
Claims (10)
1. a high security lithium ion cell negative electrode material is characterized in that, processes through following steps:
(1) preparation Al (OH)
3Colloidal sol
With AlCl
3At 200～300 ℃ of pyrogenically prepared aluminium chlorides, afterwards aluminium chloride is used deionized water dissolving, filter, obtain filtrating, in said filtrating, add organic dispersing agent solution and ammonium salt, under 40～90 ℃ of temperature, react 6～48h afterwards, make Al (OH)
3Colloidal sol;
(2) preparation graphite/LiAlO
2Composite granule
The Al (OH) that step (1) is made
3Colloidal sol mixes with NaOH, LiOH, under 40～90 ℃ of temperature, reacts 6～48h, and cooling afterwards makes and contains LiAlO
2Mixed liquor, afterwards graphite is added the said LiAlO of containing
2In the mixed liquor and be uniformly dispersed; Get dispersed system A, the pH value with said dispersed system A transfers to 7～9 then, gets even colloidal sol compound system; Heat said even colloidal sol compound system down at 500～800 ℃ afterwards; Steam the organic dispersing agent and the moisture that remove in the said even colloidal sol compound system, get solids, grind said solids afterwards and obtain graphite/LiAlO
2Composite granule;
(3) preparation graphite/LiAlO
2/ carbon nano tube compound material
Graphite/LiAlO that step (2) is made
2Composite granule, iron catalyst are put into quartz ampoule, and heated quarty tube and in quartz ampoule, feed nitrogen is closed nitrogen when being warming up to 800～1000 ℃ then; Logical hydrogen in said quartz ampoule, duration of ventilation is 1～2 hour, temperature remains 800～1000 ℃; Close hydrogen afterwards, logical acetylene or methane gas in said quartz ampoule, duration of ventilation is 1～2 hour; Temperature remains 800～1000 ℃; Close acetylene or methane gas afterwards, in said quartz ampoule, feed nitrogen to said quartz ampoule again and be cooled to room temperature, make graphite/LiAlO
2/ carbon nano tube compound material, said graphite/LiAlO
2/ carbon nano tube compound material obtains the high security lithium ion cell negative electrode material again through ball milling.
2. high security lithium ion cell negative electrode material according to claim 1 is characterized in that, the concentration of said filtrating is 0.1～1.0mol/L.
3. high security lithium ion cell negative electrode material according to claim 1 is characterized in that, the aqueous solution or polyvinyl alcohol water solution that said organic dispersing agent solution is polyethylene glycol, the mass percent concentration of said organic dispersing agent solution are 20～50%.
4. high security lithium ion cell negative electrode material according to claim 1 is characterized in that, said ammonium salt is ammonium chloride or ammonium sulfate.
5. high security lithium ion cell negative electrode material according to claim 1 is characterized in that, in the step (1), and AlCl
3Quality, organic dispersing agent solution in the ratio of quality of quality and ammonium salt of contained organic dispersing agent be: AlCl
3Quality: the quality of contained organic dispersing agent in the organic dispersing agent solution: the quality of ammonium salt=1: (0.1～0.3): (0.2～0.5).
6. high security lithium ion cell negative electrode material according to claim 1 is characterized in that, Al (OH) in the step (2)
3Al in the colloidal sol (OH)
3, with the mol ratio of NaOH, LiOH be: Al (OH)
3: NaOH: LiOH=1: (1～1.5): (1～1.5).
7. high security lithium ion cell negative electrode material according to claim 1 is characterized in that, graphite and LiAlO in the step (2)
2Mass ratio be: graphite: LiAlO
2=1: (0.01～0.1).
8. according to claim 1 or 7 described high security lithium ion cell negative electrode materials, it is characterized in that said graphite is Delanium or carbonaceous mesophase spherules.
9. high security lithium ion cell negative electrode material according to claim 1 is characterized in that, graphite/LiAlO in the step (3)
2The mass ratio of composite granule and iron catalyst is: graphite/LiAlO
2Composite granule: iron catalyst=1: (0.01～1).
10. the preparation method of the described high security lithium ion cell negative electrode material of claim 1 is characterized in that, may further comprise the steps:
(1) preparation Al (OH)
3Colloidal sol
With AlCl
3At 200～300 ℃ of pyrogenically prepared aluminium chlorides, afterwards aluminium chloride is used deionized water dissolving, filter, obtain filtrating, in said filtrating, add organic dispersing agent solution and ammonium salt, under 40～90 ℃ of temperature, react 6～48h afterwards, make Al (OH)
3Colloidal sol;
(2) preparation graphite/LiAlO
2Composite granule
The Al (OH) that step (1) is made
3Colloidal sol mixes with NaOH, LiOH, under 40～90 ℃ of temperature, reacts 6～48h, makes LiAlO
2, afterwards graphite is added said LiAlO
2In and be uniformly dispersed; Get dispersed system A, the pH value with said dispersed system A transfers to 7～9 then, gets even colloidal sol compound system; Heat said even colloidal sol compound system down at 500～800 ℃ afterwards; Steam the organic dispersing agent and the moisture that remove in the said even colloidal sol compound system, get solids, grind said solids afterwards and obtain graphite/LiAlO
2Composite granule;
(3) preparation graphite/LiAlO
2/ carbon nano tube compound material
Graphite/LiAlO that step (2) is made
2Composite granule, iron catalyst are put into quartz ampoule, and heated quarty tube and in quartz ampoule, feed nitrogen is closed nitrogen when being warming up to 800～1000 ℃ then; Logical hydrogen in said quartz ampoule, duration of ventilation is 1～2 hour, temperature remains 800～1000 ℃; Close hydrogen afterwards, logical acetylene or methane gas in said quartz ampoule, duration of ventilation is 1～2 hour; Temperature remains 800～1000 ℃; Close acetylene or methane gas afterwards, in said quartz ampoule, feed nitrogen to said quartz ampoule again and be cooled to room temperature, make graphite/LiAlO
2/ carbon nano tube compound material, said graphite/LiAlO
2/ carbon nano tube compound material obtains the high security lithium ion cell negative electrode material again through ball milling.
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