CN102651472B - Composite cathode material of lithium ion battery and preparation method thereof - Google Patents
Composite cathode material of lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN102651472B CN102651472B CN201210169192.XA CN201210169192A CN102651472B CN 102651472 B CN102651472 B CN 102651472B CN 201210169192 A CN201210169192 A CN 201210169192A CN 102651472 B CN102651472 B CN 102651472B
- Authority
- CN
- China
- Prior art keywords
- zinc
- lithium ion
- iron
- cathode material
- composite cathode
- 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.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 60
- 239000010406 cathode material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 34
- 239000011701 zinc Substances 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims description 55
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 27
- 150000001721 carbon Chemical group 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000012266 salt solution Substances 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000000498 ball milling Methods 0.000 claims description 20
- 150000002505 iron Chemical class 0.000 claims description 20
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 17
- 150000003751 zinc Chemical class 0.000 claims description 17
- 239000011159 matrix material Substances 0.000 claims description 16
- 239000005416 organic matter Substances 0.000 claims description 16
- 238000000197 pyrolysis Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000007711 solidification Methods 0.000 claims description 9
- 230000008023 solidification Effects 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 7
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- PIFBJINVDJJYCV-UHFFFAOYSA-J dizinc tetraacetate Chemical compound [Zn+2].[Zn+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O PIFBJINVDJJYCV-UHFFFAOYSA-J 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 abstract description 9
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000009830 intercalation Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 2
- 239000002296 pyrolytic carbon Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 35
- 238000013019 agitation Methods 0.000 description 23
- 239000002245 particle Substances 0.000 description 20
- 238000000227 grinding Methods 0.000 description 15
- 238000003760 magnetic stirring Methods 0.000 description 13
- 229910044991 metal oxide Inorganic materials 0.000 description 11
- 150000004706 metal oxides Chemical class 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 239000011149 active material Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000006253 efflorescence Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 206010037844 rash Diseases 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910013391 LizN Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052718 tin Inorganic materials 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a composite cathode material of a lithium ion battery and a preparation method thereof, and mainly aims to improve the electrical chemical performance of the composite cathode material of the lithium ion battery. The composite cathode material of the lithium ion battery is a composite material formed by ZnO and FeO, or the composite material formed by coating ZnO and FeO by porous carbon C. The preparation method comprises the steps of: mixing to obtain a ferrite-zinc mixed solution, adding an organic pyrolytic carbon precursor into the ferrite-zinc mixed solution, preserving heat and solidifying, and sintering at a constant temperature. Compared with the prior art, by adopting the invention, the excellent de-lithium-intercalation ability, higher specific capacity and excellent cycling stability of transition metal oxide can be kept; the first reversible specific capacity is more than 700mAh/g, and the reversible specific capacity is more than 400mAh/g after cycling for 80 weeks; the composite cathode material is simple in manufacturing method, low in cost, little in environment pollution, and applicable to the cathode material of the lithium ion battery for lithium ion storage batteries, power batteries, various portable device, electrical tools and the like.
Description
Technical field
The present invention relates to a kind of cell negative electrode material and preparation method thereof, particularly a kind of lithium ion battery cathode material and its preparation method.
Background technology
Since Gaston Plante in 1859 proposes the concept of lead-acid battery, chemical power source circle is attempted to develop the height ratio capacity made new advances always, the secondary cell of long circulation life.Lithium ion battery has formally come into operation whole 20 years as a kind of novel secondary battery, it has voltage high (4V), energy density is high, self discharge is little, have extended cycle life, memory-less effect, pollution-free advantage, has now been widely used on the movable equipments such as notebook computer, mobile phone, digital camera and electric motor car.
Lithium ion battery commercially available at present mainly adopts graphite-like material with carbon element as negative material, and graphite material has following shortcoming: 1, theoretical specific capacity is only 372mAh/g, and actual capacity is lower; 2, there is height-oriented layer structure, very poor with the compatibility of organic electrolyte: 3, to there is graphite linings peeling in fast charging and discharging process, cause capacity attenuation; 4, its intercalation potential closely lithium deposition potential, easily produces Li dendrite phenomenon, causes potential safety hazard.Therefore, the performance difficulty improving graphite type material is further large.In order to meet the demand of people to high-capacity battery, the high performance negative material of high power capacity of new generation must be developed.Current high-capacity cathode material mainly concentrates on two large classes: a class is pure metals and the oxide thereof of Si and Sn, or its composite material, and another kind of is metal oxide.The storage lithium mechanism of described metal oxide roughly can be divided into two kinds: 1, alloy-type mechanism, as ZnO+Li → Zn+Li
2o, Zn+Li ← → LiZn; 2, oxidation-reduction type mechanism, as FeO+Li ← → Fe+Li
2o.Metal oxide based on these two kinds of mechanism shows the gram volume doubling graphite, but there are some shortcomings: this metal oxide itself is the very poor semi-conducting material of a kind of conductivity, and the Li generated in reaction
2o is degrading conductivity more; The reaction of metal oxide and Li produces " Volumetric expansion ", removal lithium embedded there will be electrode " efflorescence " repeatedly, not only lose electrical contact with collector, but also the metallic particles of generation can be made " reunion " to occur and lose electro-chemical activity, finally cause cycle performance to decline, limit the application of this metal oxide in lithium ion battery.
Summary of the invention
The object of this invention is to provide a kind of composite cathode material for lithium ion cell and preparation method thereof, the technical problem that solve improves the chemical property of transition metal oxide composite cathode material.
The present invention is by the following technical solutions: a kind of composite cathode material for lithium ion cell, described composite cathode material for lithium ion cell is the ZnO/FeO composite material that ZnO and FeO is formed, the ratio of the amount of substance of ZnO and FeO is 1 ~ 24:8, or the ZnO/FeO/C composite material of porous carbon C clading ZnO and FeO formation, the ratio of the amount of substance of C and ZnO, FeO sum is 1 ~ 14:4, the average grain diameter of ZnO/FeO composite material and ZnO/FeO/C composite material is 10 ~ 60 μm, and specific area is 1 ~ 20m
2/ g.
A kind of preparation method of composite cathode material for lithium ion cell, comprise the following steps: one, by zinc nitrate, zinc chloride or zinc acetate zinc solution and ferric nitrate, iron chloride or ironic citrate iron salt solutions, by the ratio 1 ~ 24:8 of zinc salt with molysite amount of substance, be mixed to get iron zinc mixed solution; Two, added by organic matter pyrolysis carbon matrix precursor in iron zinc mixed solution, temperature is 50 ~ 100 DEG C, and rotating speed is 10 ~ 25r/min, stirs 30 ~ 180min, obtains even slurry; Described organic matter pyrolysis carbon matrix precursor is more than one in citric acid, glucose, phenolic resins, epoxy resin and sucrose, organic matter pyrolysis carbon matrix precursor presses the ratio of carbon atom and the amount of zinc-iron atom species, for (0 < carbon atom amount of substance≤1): (amounts of 4 zinc-iron atom species), or (amount of 1 < carbon atom amount of substance≤14:4 zinc-iron atom species); Three, by even slurry with 0.5 ~ 3 DEG C/min heating rate from room temperature to 50 ~ 200 DEG C, heat preservation solidification 5 ~ 48h, naturally cools to room temperature in stove; Four, at protective atmosphere nitrogen or argon gas; flow is under 0.9 ~ 2L/min condition; with 0.5 ~ 5 DEG C/min heating rate from room temperature to 700 ~ 900 DEG C; Isothermal sinter 14 ~ 24h; room temperature is naturally cooled in stove; obtaining composite cathode material for lithium ion cell, is the ZnO/FeO composite material that ZnO and FeO is formed, or the ZnO/FeO/C composite material of porous carbon C clading ZnO and FeO formation.
Heat preservation solidification 5 ~ 48h of the present invention, after naturally cooling to room temperature, puts into planetary ball mill in stove, ball milling 2 ~ 10h, and ball material mass ratio is 10 ~ 20:1, and ball material is stainless shot, and diameter is 10mm, obtains the powder that average grain diameter is 10 ~ 200 μm.
Isothermal sinter 14 ~ 24h of the present invention, after naturally cooling to room temperature, puts into planetary ball mill in stove, ball milling 2 ~ 10h, ball material mass ratio is 10 ~ 20:1, and ball material is stainless shot, diameter is 10mm, and sieving through 200 orders obtains the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μm.
Zinc nitrate, zinc chloride or zinc acetate are that 0.1 ~ 10mol/L is dissolved in deionized water by zinc atom concentration by the present invention, obtain zinc solution; Be that 0.1 ~ 10mol/L is dissolved in deionized water by ferric nitrate, iron chloride or ironic citrate by iron atom concentration, obtain iron salt solutions.
Zinc nitrate, zinc chloride or zinc acetate are that 0.1 ~ 10mol/L is dissolved in deionized water by zinc atom concentration by the present invention, and temperature is 25 ~ 50 DEG C, and rotating speed is 10 ~ 25r/min, and the time is 30 ~ 180min; Described is that 0.1 ~ 10mol/L is dissolved in deionized water by ferric nitrate, iron chloride or ironic citrate by iron atom concentration, and temperature is 25 ~ 50 DEG C, and rotating speed is 10 ~ 25r/min, and the time is 30 ~ 180min.
Of the present invention by zinc solution and iron salt solutions, be 10 ~ 50 DEG C in temperature, rotating speed is 10 ~ 25r/min, and the time is be mixed to get iron zinc mixed solution under 30 ~ 180min condition.
When organic matter pyrolysis carbon matrix precursor of the present invention is two or more, often kind of material adds respectively, respectively under rotating speed is 10 ~ 25r/min, stirs 30 ~ 180min.
Step one of the present invention, by the ratio 1.6 ~ 8:8 of zinc salt with molysite amount of substance; Described step 2, temperature is 70 ~ 100 DEG C, rotating speed is 10 ~ 15r/min, stir 30 ~ 120min, organic matter pyrolysis carbon matrix precursor presses the ratio of carbon atom and the amount of zinc-iron atom species, be 0.08 < carbon atom amount of substance≤0.96:4, or 2.12 < carbon atom amount of substance≤13.44:4; Described step 3, with 1 ~ 3 DEG C/min heating rate from room temperature to 100 ~ 150 DEG C, heat preservation solidification 5 ~ 24h; Described step 4, flow is 0.9 ~ 1.5L/min, with 0.5 ~ 4 DEG C/min heating rate from room temperature to 700 ~ 750 DEG C.
Step one of the present invention, by the ratio 4:8 of zinc salt with molysite amount of substance; Described step 2, temperature is 90 DEG C, and rotating speed is 15r/min, stirs 90min, and organic matter pyrolysis carbon matrix precursor presses the ratio of carbon atom and the amount of zinc-iron atom species, is 0.8:4, or 9.92:4; Described step 3, with 2 DEG C/min heating rate from room temperature to 110 DEG C, heat preservation solidification 12h; Described step 4, flow is 1L/min, with 3 DEG C/min heating rate from room temperature to 700 DEG C, Isothermal sinter 24h.
The present invention compared with prior art, by preparing the composite negative pole material of transition metal oxide, and under particle diameter is micron-sized situation, the removal lithium embedded ability that transition metal oxide is good can be kept, higher specific capacity and good cyclical stability, reversible specific capacity is greater than 700mAh/g first, circulate and remain on more than 400mAh/g in 80 weeks, through mixing, heat treatment, grinding steps, manufacture method is simple, cost is low, environmental pollution is little, be applicable to lithium-ion energy storage battery, electrokinetic cell, various portable device, the lithium ion battery negative material such as electric tool, there is good industrialization prospect.
Accompanying drawing explanation
Fig. 1 is the SEM picture of the ZnO/FeO/C composite negative pole material of embodiment 1.
Fig. 2 is the XRD collection of illustrative plates of the ZnO/FeO/C composite negative pole material of embodiment 1.
Fig. 3 is the charging and discharging curve of the ZnO/FeO/C composite negative pole material of embodiment 1.
Fig. 4 is the cycle performance curve of the ZnO/FeO/C composite negative pole material of embodiment 1.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.Composite cathode material for lithium ion cell of the present invention, for the ZnO/FeO composite material that ZnO and FeO is formed, the ratio of the amount of substance of ZnO and FeO is 1 ~ 24:8, or the ZnO/FeO/C composite material of porous carbon C clading ZnO and FeO formation, the ratio of the amount of substance of C and ZnO, FeO sum is 1 ~ 14:4, the average grain diameter of ZnO/FeO composite material and ZnO/FeO/C composite material is 10 ~ 60 μm, and specific area is 1 ~ 20m2/g.
The preparation method of composite cathode material for lithium ion cell of the present invention, comprises the following steps:
One, be that 0.1 ~ 10mol/L is dissolved in deionized water by zinc salt by zinc atom concentration, magnetic agitation, temperature is 25 ~ 50 DEG C, and rotating speed is 10 ~ 25r/min, and the time is 30 ~ 180min, dissolves completely to zinc salt, obtains zinc solution.Be that 0.1 ~ 10mol/L is dissolved in deionized water by molysite by iron atom concentration, magnetic agitation, temperature is 25 ~ 50 DEG C, and rotating speed is 10 ~ 25r/min, and the time is 30 ~ 180min, dissolves completely to molysite, obtains iron salt solutions.
Zinc salt is zinc nitrate, zinc chloride or zinc acetate.
Molysite is ferric nitrate, iron chloride or ironic citrate.
Two, by zinc solution and iron salt solutions, by the ratio 1 ~ 24:8 of zinc salt with molysite amount of substance, be 10 ~ 50 DEG C in temperature, rotating speed is 10 ~ 25r/min, and the time is that 30 ~ 180min condition lower magnetic force is uniformly mixed, and obtains iron zinc mixed solution.
Three, added by organic matter pyrolysis carbon matrix precursor in iron zinc mixed solution, temperature is 50 ~ 100 DEG C, and rotating speed is 10 ~ 25r/min, and temperature constant magnetic stirring 30 ~ 180min, obtains even slurry.
Organic matter pyrolysis carbon matrix precursor is more than one in citric acid, glucose, phenolic resins, epoxy resin and sucrose.When the organic matter pyrolysis carbon matrix precursor added is two or more, often kind of material can add at the same temperature respectively, respectively under rotating speed is 10 ~ 25r/min, and temperature constant magnetic stirring 30 ~ 180min.
Organic matter pyrolysis carbon matrix precursor presses carbon atom and the ratio of the amount of zinc-iron atom species, when (0 < carbon atom amount of substance≤1): time (amounts of 4 zinc-iron atom species), obtains the ZnO/FeO composite material that ZnO and FeO is formed after sintering; When (amount of 1 < carbon atom amount of substance≤14:4 zinc-iron atom species), after sintering, obtain the ZnO/FeO/C composite material of porous carbon C clading ZnO and FeO formation.Because when carbon amounts is less, all carbon participates in ferric reduction reaction and generates CO
2gas is excluded, and noresidue carbon exists; When carbon amounts is more, only part carbon participates in ferric reduction reaction and is excluded, and has residual carbon to exist.
Four, even slurry is moved in baking oven, be warming up to 50 ~ 200 DEG C, heat preservation solidification 5 ~ 48h with 0.5 ~ 3 DEG C/min heating rate from room temperature (20 DEG C), make slurry become xerogel, in stove, naturally cool to room temperature.
Five, cooled material is put into planetary ball mill; ball milling 2 ~ 10h; ball material mass ratio is 10 ~ 20:1; ball material is stainless shot; diameter is 10mm; obtain the powder that average grain diameter is 10 ~ 200 μm; again powder is moved in the SHFB96/16 type Muffle furnace of sigma (Shanghai) high-temperature electric resistance furnace Co., Ltd or the batch (-type) rotary furnace of Japanese Takasago Kogyo KK; under protective atmosphere; 700 ~ 900 DEG C are warming up to from room temperature (20 DEG C) with 0.5 ~ 5 DEG C/min heating rate; Isothermal sinter 14 ~ 24h, naturally cools to room temperature in stove.
Protective gas is nitrogen or argon gas, and flow is 0.9 ~ 2L/min.
Six, again planetary ball mill is put into after cooling, ball milling 2 ~ 10h, ball material mass ratio is 10 ~ 20:1, ball material is stainless shot, diameter is 10mm, last powder sieves through 200 orders and obtains the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μm, and composite cathode material for lithium ion cell is the ZnO/FeO composite material that ZnO and FeO is formed, or the ZnO/FeO/C composite material of porous carbon C clading ZnO and FeO formation.
Composite material ZnO/FeO prepared by the inventive method is based on two kinds of metal oxides, the storage lithium feature of two kinds of metal oxides comes from alloy-type mechanism and oxidation-reduction type mechanism respectively, although all there is Study of Volume Expansion in the process of removal lithium embedded, but both coefficients of cubical expansion are different with spring factor, all can be used as the volume buffer of the other side, make electrode material not easily efflorescence, optimize the cycle performance of single metal oxide to a certain extent.Another composite material ZnO/FeO/C that the inventive method obtains is that material with carbon element itself has high conductivity based on porous carbon clading ZnO and FeO, so the coated conductivity that improve metal oxide of carbon, active material can be made to participate in electrode reaction faster; On the other hand, porous carbon to be present between two kinds of metal oxides as two-phase volume expansion buffer space, inhibits the efflorescence of electrode material and the reunion of active material, significantly increases cyclical stability.
Composite cathode material for lithium ion cell prepared by the inventive method, with Japanese Hitachi-S4800 scanning electronic microscope observation composite material surface pattern, its composition, structure is measured with Dutch Panalytical X ' pert PRO X-ray diffraction analysis instrument, its particle diameter is measured with Britain's Malvern Mastersizer 2000 laser particle size analyzer, by the BET method of nitrogen adsorption, U.S.'s health tower Nova 1000e specific area/Porosimetry measures its specific area.
With the composite cathode material for lithium ion cell that the inventive method prepares, make the active material of lithium ion battery negative material, carbon black Super P is conductive agent, and Kynoar PVDF is that binding agent obtains electrode material.Three according to the proportioning of quality is: active material: conductive agent: binding agent=8:1:1, adding appropriate 1-METHYLPYRROLIDONE (NMP) wherein adopts paste mixer to mix well into pasty state, then adopt coating machine coating on Copper Foil, coating thickness is 200 μm, is punching into the pole piece that diameter is 8.4mm after oven dry.Be to electrode with pour lithium slice, this pole piece is work electrode, and (positive pole stainless steel gasket diameter is 8.4mm to adopt Celgard 2400 barrier film in German Braun glove box, be assembled into die type; Negative pole copper backing diameter is 11.4mm) simulated battery.Electrolyte adopts the solution of 1M LiPF6/EC+DMC, and wherein ethylene carbonate EC and dimethyl carbonate DMC volume ratio are 1:1.With Wuhan gold promise Land CT 2001A charge-discharge test cabinet, in the voltage range of 0.001 ~ 3V, carry out the test of simulated battery charge-discharge performance with the current density of 100mA/g.
Embodiment 1
One, 74.37g(0.25mol is taken) Zn (NO
3)
26H
2o is dissolved in 300ml deionized water, temperature 25 DEG C, and rotating speed 10r/min, magnetic agitation 180min obtain the zinc solution that zinc atom concentration is 0.83mol/L.Take 202g(0.5mol again) Fe (NO
3)
3.9H
2o is dissolved in another 300ml deionized water, temperature 25 DEG C, and rotating speed 10r/min, magnetic agitation 180min obtain the iron salt solutions that iron atom concentration is 1.67mol/L.
Two, mixed with iron salt solutions by zinc solution, zinc salt and molysite mol ratio are 1:2, temperature 25 DEG C, and rotating speed 10r/min, magnetic agitation 180min obtain iron zinc mixed solution.
Three, in iron zinc mixed solution, slowly 52.535g(0.25mol is added) C
6h
8o
7h
2o, at 50 DEG C, rotating speed 10r/min, temperature constant magnetic stirring 120min, then add 11.88g(0.06mol wherein) C
6h
12o
6h
2o, then at 50 DEG C, rotating speed 10r/min, temperature constant magnetic stirring 120min, obtains even slurry, the mol ratio of carbon atom and zinc-iron atom is 9.92:4.
Four, move in baking oven by even slurry, with 0.5 DEG C/min heating rate from room temperature to 110 DEG C, insulation 24h, naturally cools to room temperature in stove.
Five, material is put into planetary ball mill, ball milling 2h, ratio of grinding media to material is 20:1, and obtain powder and move in Muffle furnace, argon flow amount is 0.9L/min, and with 0.5 DEG C/min heating rate from room temperature to 750 DEG C, heat treatment 24h, cools in stove naturally.
Six, again powder is put into planetary ball mill, ball milling 2h, ratio of grinding media to material is 20:1, and the 200 order mesh that sieved by powder obtain the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μm.
As shown in Figure 1, the composite cathode material for lithium ion cell of embodiment 1, for porous C clading ZnO and FeO particle form heterogeneous mixed uniformly compound system.Particle diameter is D
10=3.55 μm, D
50=16.46 μm, D
90=41.57 μm, specific area is 6.2m
2/ g, wherein ZnO is cross section is hexagonal Wurzite structure, and FeO presents irregular contour structures.
As shown in Figure 2, the composite cathode material for lithium ion cell XRD collection of illustrative plates of embodiment 1 represents the compound of ZnO and FeO, exists without dephasign, because carbon coated material is amorphous phase, so there is not corresponding diffraction maximum in collection of illustrative plates.
As shown in Figure 3, the composite cathode material for lithium ion cell of embodiment 1 is adopted to make simulated battery, in the voltage range of 0.001 ~ 3V, carry out charge-discharge test with the current density of 100mA/g, first discharge specific capacity reaches 1064mAh/g, has the platform that very long near 0.75V, initial charge specific capacity reaches 707mAh/g, initial coulomb efficiency is 67%, and coulombic efficiency subsequently all more than 98%, and is tending towards 100% gradually along with circulation coulombic efficiency.
As shown in Figure 4, through the circulation of 80 times, charging and discharging capacity is stabilized in more than 400mAh/g, illustrates that this composite material has good cyclical stability.Electrochemical property test the results are shown in Table 1.
Embodiment 2
One, 67.9g(0.5mol is taken) ZnCl
2be dissolved in 300ml deionized water, temperature 50 C, rotating speed 25r/min, magnetic agitation 30min, obtain the zinc solution that zinc atom concentration is 1.67mol/L.Take 202g(0.5mol again) Fe (NO
3)
39H
2o is dissolved in another 300ml deionized water, temperature 50 C, and rotating speed 25r/min, magnetic agitation 30min obtain the iron salt solutions that iron atom concentration is 1.67mol/L.
Two, mixed with iron salt solutions by zinc solution, zinc salt and molysite mol ratio are 1:1, temperature 50 C, rotating speed 25r/min, magnetic agitation 30min, obtain iron zinc mixed solution.
Three, in iron zinc mixed solution, slowly 105g(0.5mol is added) C
6h
8o
7h
2o, at 70 DEG C, rotating speed 25r/min, temperature constant magnetic stirring 30min, then add 12g(0.06mol wherein) C
6h
12o
6h
2o, then at 70 DEG C, rotating speed 25r/min, temperature constant magnetic stirring 30min, obtains even slurry, the mol ratio of carbon atom and zinc-iron atom is 13.44:4.
Four, move in baking oven by even slurry, with 3 DEG C/min heating rate from room temperature to 50 DEG C, insulation 48h, naturally cools to room temperature in stove.
Five, material is put into planetary ball mill, ball milling 10h, ratio of grinding media to material is 10:1, obtains powder, then moves in rotary furnace by powder, and nitrogen flow is 2L/min, and with 0.5 DEG C/min heating rate from room temperature to 900 DEG C, heat treatment 14h, cools in stove naturally.
Six, ball milling 10h, ratio of grinding media to material is 10:1, obtains powder, and the 200 order mesh that sieve obtain the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μm.
This composite cathode material for lithium ion cell is made up of porous carbon materials clading ZnO and FeO particle.Its particle diameter is D
10=3.8 μm, D
50=13.55 μm, D
90=39.87 μm, specific area is 6.9m
2/ g.After adopting the composite cathode material for lithium ion cell of embodiment 2 to make simulated battery, carry out electrochemical property test, the results are shown in Table 1.
Embodiment 3
One, 45.9g(0.25mol is taken) Zn (CH
3cOO)
22H
2o is dissolved in 50ml deionized water, temperature 40 DEG C, and rotating speed 15r/min, magnetic agitation 100min obtain the zinc solution that zinc atom concentration is 5mol/L.Take 324.42g(2mol again) FeCl
3be dissolved in another 200ml deionized water, temperature 40 DEG C, rotating speed 15r/min, magnetic agitation 100min, obtain the iron salt solutions that iron atom concentration is 10mol/L.
Two, mixed with iron salt solutions by zinc solution, zinc salt and molysite mol ratio are 1:8, temperature 40 DEG C, and rotating speed 15r/min, magnetic agitation 100min obtain iron zinc mixed solution.
Three, in iron zinc mixed solution, slowly 34.23g(0.1mol is added) C
12h
22o
11, at 100 DEG C, rotating speed 15r/min, temperature constant magnetic stirring 30min, obtains even slurry, and the mol ratio of carbon atom and zinc-iron atom is 2.12:4.
Four, move in baking oven by even slurry, with 1 DEG C/min heating rate from room temperature to 200 DEG C, insulation 5h, naturally cools to room temperature in stove.
Five, material is put into planetary ball mill, ball milling 5h, ratio of grinding media to material is 15:1, obtains powder, then moves in rotary furnace by powder, and nitrogen flow is 1.5L/min, and with 5 DEG C/min heating rate from room temperature to 700 DEG C, heat treatment 24h, cools in stove naturally.
Six, ball milling 5h, ratio of grinding media to material is 15:1, obtains powder, and the 200 order mesh that sieve obtain the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μm.
This composite material is made up of porous carbon materials clading ZnO and FeO particle.Its particle diameter is D
10=14.81 μm, D
50=32.86 μm, D
90=61.23 μm, its specific area is 4.12m
2/ g.After adopting the composite cathode material for lithium ion cell of embodiment 3 to make simulated battery, carry out electrochemical property test, the results are shown in Table 1.
Embodiment 4
One, 45.9g(0.25mol is taken) Zn (CH
3cOO)
22H
2o is dissolved in 50ml deionized water, temperature 40 DEG C, and rotating speed 15r/min, magnetic agitation 100min obtain the zinc solution that zinc atom concentration is 5mol/L.Take 324.42g(2mol again) FeCl
3be dissolved in another 200ml deionized water, temperature 40 DEG C, rotating speed 15r/min, magnetic agitation 100min, obtain the iron salt solutions that iron atom concentration is 10mol/L.
Two, mixed with iron salt solutions by zinc solution, zinc salt and molysite mol ratio are 1:8, temperature 40 DEG C, and rotating speed 15r/min, magnetic agitation 100min obtain iron zinc mixed solution.
Three, in iron zinc mixed solution, slowly 17.11g(0.05mol is added) C
12h
22o
11, at 100 DEG C, rotating speed 15r/min, temperature constant magnetic stirring 30min, obtains even slurry, and the mol ratio of carbon atom and zinc-iron atom is 1.07:4.
Four, move in baking oven by even slurry, with 1 DEG C/min heating rate from room temperature to 200 DEG C, insulation 5h, naturally cools to room temperature in stove.
Five, material is put into planetary ball mill, ball milling 5h, ratio of grinding media to material is 15:1, obtains powder, then moves in rotary furnace by powder, and nitrogen flow is 1.5L/min, and with 5 DEG C/min heating rate from room temperature to 700 DEG C, heat treatment 24h, cools in stove naturally.
Six, ball milling 5h, ratio of grinding media to material is 15:1, obtains powder, and the 200 order mesh that sieve obtain the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μm.
This composite material is made up of porous carbon materials clading ZnO and FeO particle.Its particle diameter is D
10=13.7 μm, D
50=30.26 μm, D
90=50.5 μm, its specific area is 4.85m
2/ g.After adopting the composite cathode material for lithium ion cell of embodiment 4 to make simulated battery, carry out electrochemical property test, the results are shown in Table 1.
Embodiment 5
One, 223.1g(0.75mol is taken) Zn (NO
3)
26H
2o is dissolved in 75ml deionized water, temperature 30 DEG C, and rotating speed 15r/min, magnetic agitation 90min obtain the zinc solution that zinc atom concentration is 10mol/L.Take 61.2g(0.25mol again) FeC
6h
5o
7be dissolved in another 2.5L deionized water, temperature 30 DEG C, rotating speed 15r/min, magnetic agitation 90min, obtain the iron salt solutions that iron atom concentration is 0.1mol/L.
Two, mixed with iron salt solutions by zinc solution, zinc salt and molysite mol ratio are 3:1, temperature 30 DEG C, and rotating speed 15r/min, magnetic agitation 90min obtain iron zinc mixed solution.
Three, in iron zinc mixed solution, slowly 7.92g(0.04mol is added) C
6h
12o
6h
2o, at 90 DEG C, rotating speed 15r/min, temperature constant magnetic stirring 180min, obtains even slurry, and the mol ratio of carbon atom and zinc-iron atom is 0.96:4.
Four, move in baking oven by even slurry, with 3 DEG C/min heating rate from room temperature to 100 DEG C, insulation 24h, naturally cools to room temperature in stove.
Five, material is put into planetary ball mill, ball milling 2h, ratio of grinding media to material is 20:1, obtains powder, then moves in Muffle furnace by powder, and nitrogen flow is 1L/min, and with 4 DEG C/min heating rate from room temperature to 700 DEG C, heat treatment 24h, cools in stove naturally.
Six, ball milling 2h, ratio of grinding media to material is 20:1, obtains powder, and the 200 order mesh that sieve obtain the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μm.
This composite material is directly made up of ZnO and FeO particle, does not have the coated phenomenon of carbon.Its particle diameter is D
10=20.15 μm, D
50=43.16 μm, D
90=70.23 μm, its specific area is 3.55m
2/ g.After adopting the composite cathode material for lithium ion cell of embodiment 5 to make simulated battery, carry out electrochemical property test, the results are shown in Table 1.
Embodiment 6
One, 27.24g(0.2mol is taken) ZnC
12be dissolved in 2L deionized water, temperature 40 DEG C, rotating speed 15r/min, magnetic agitation 100min, obtain the zinc solution that zinc atom concentration is 0.1mol/L.Take 162.21g(1mol again) FeCl
3be dissolved in another 300ml deionized water, temperature 40 DEG C, rotating speed 15r/min, magnetic agitation 100min, obtain the iron salt solutions that iron atom concentration is 3.34mol/L.
Two, mixed with iron salt solutions by zinc solution, zinc salt and molysite mol ratio are 1:5, temperature 40 DEG C, and rotating speed 15r/min, magnetic agitation 100min obtain iron zinc mixed solution.
Three, in iron zinc mixed solution, slowly 3.96g(0.02mol is added) C
6h
12o
6h
2o, at 100 DEG C, rotating speed 10r/min, temperature constant magnetic stirring 90min, then add 4.2g(0.02mol wherein) C
6h
8o
7h
2o, then at 100 DEG C, rotating speed 10r/min, temperature constant magnetic stirring 90min, obtains even slurry, the mol ratio of carbon atom and zinc-iron atom is 0.8:4.
Four, move in baking oven by even slurry, with 2 DEG C/min heating rate from room temperature to 150 DEG C, insulation 12h, naturally cools to room temperature in stove.
Five, material is put into planetary ball mill, ball milling 2h, ratio of grinding media to material is 10:1, obtains powder, then moves in rotary furnace by powder, and nitrogen flow is 1L/min, and with 3 DEG C/min heating rate from room temperature to 700 DEG C, heat treatment 24h, cools in stove naturally.
Six, ball milling 8h, ratio of grinding media to material is 10:1, obtains powder, and the 200 order mesh that sieve obtain the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μm.
This composite material is directly made up of ZnO and FeO particle, does not have the coated phenomenon of carbon.Its particle diameter is D
10=18.24 μm, D
50=30.27 μm, D
90=62.45 μm, its specific area is 4.67m
2/ g, after adopting the composite cathode material for lithium ion cell of embodiment 6 to make simulated battery, carries out electrochemical property test, the results are shown in Table 1.
Embodiment 7
One, 27.24g(0.2mol is taken) ZnC
l2be dissolved in 2L deionized water, temperature 40 DEG C, rotating speed 15r/min, magnetic agitation 100min, obtaining zinc atom concentration is 0.1mol/L zinc solution.Take 162.21g(1mol again) FeCl
3be dissolved in another 300ml deionized water, temperature 40 DEG C, rotating speed 15r/min, magnetic agitation 100min, obtaining iron atom concentration is 3.34mol/L iron salt solutions.
Two, mixed with iron salt solutions by zinc solution, zinc salt and molysite mol ratio are 1:5, temperature 40 DEG C, and rotating speed 15r/min, magnetic agitation 100min obtain iron zinc mixed solution.
Three, in iron zinc mixed solution, slowly 0.396g(0.002mol is added) C
6h
12o
6h
2o, at 100 DEG C, rotating speed 10r/min, temperature constant magnetic stirring 90min, then add 0.42g(0.002mol wherein) C
6h
8o
7h
2o, then at 100 DEG C, rotating speed 10r/min, temperature constant magnetic stirring 90min, obtains even slurry, the mol ratio of carbon atom and zinc-iron atom is 0.08:4.
Four, move in baking oven by even slurry, with 2 DEG C/min heating rate from room temperature to 150 DEG C, insulation 12h, naturally cools to room temperature in stove.
Five, material is put into planetary ball mill, ball milling 2h, ratio of grinding media to material is 10:1, obtains powder, then moves in rotary furnace by powder, and nitrogen flow is 1L/min, and with 3 DEG C/min heating rate from room temperature to 700 DEG C, heat treatment 24h, cools in stove naturally.
Six, ball milling 8h, ratio of grinding media to material is 10:1, obtains powder, and the 200 order mesh that sieve obtain the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μm.
This composite material is directly made up of ZnO and FeO particle, does not have the coated phenomenon of carbon.Its particle diameter is D
10=16.4 μm, D
50=26.7 μm, D
90=52.85 μm, its specific area is 4.96m
2/ g, after adopting the composite cathode material for lithium ion cell of embodiment 7 to make simulated battery, carries out electrochemical property test, the results are shown in Table 1.
Comparative example 1, makes the active material of lithium ion battery negative material after 200 order mesh sieve with commercially available ZnO powder, make simulated battery, carry out electrochemical property test, the results are shown in Table 1 by the method identical with embodiment by the method identical with embodiment.
Comparative example 2, " preparation of carbon, ZnO/ carbon porous microsphere and the application study on lithium ion battery negative thereof " (Cao Yang, Central China Normal University's master thesis, 2009) nano ZnO particles described in is as lithium ion battery negative material active material, and its electrochemical property test results contrast is in table 1.
Comparative example 3, " Nano-sized transition-metal oxides asnegative-electrode materials forlithium-ion batteries " (lithium ion battery nano transition metal oxides makes negative material, P.Poizot, S.Laruelle, S.Grugeon et al.Nature, 2000,407:496 ~ 499) described in FeO particle as lithium ion battery negative material active material, its electrochemical property test results contrast is in table 1.
Found out by the test result of table 1, the reversible capacity first of embodiment 1,2,3 and 4 is at 702.9 ~ 745mAh/g, and the 50 weeks reversible specific capacities that circulate remain on more than 412.7mAh/g, and capability retention is more than 55.7%.The reversible capacity first that embodiment 5,6 and 7 obtains is all at more than 811.6mAh/g, and comparatively embodiment 1,2,3 and 4 wants high, but circulation 50 weeks later below capacity 403.8mAh/g, conservation rate below 50%, comparatively embodiment 1,2,3 and 4 low.The reversible capacity first that comparative example 1,2 and 3 obtains is all at 500 ~ 760mAh/g, and the 50 weeks reversible specific capacities that circulate are at below 371mAh/g, all low than 50 weeks reversible specific capacities in embodiment.As can be seen here, although two kinds of composite cathode material for lithium ion cell ZnO/FeO and ZnO/FeO/C of the present invention are micron particles, but comparing single nanocrystalline transition metal oxide, still to show specific capacity high, have extended cycle life, stability is good, so composite material of the present invention is more suitable for the negative material of energy-storage battery and electrokinetic cell.
The electrochemical property test of table 1 embodiment and comparative example
Claims (9)
1. the preparation method of a composite cathode material for lithium ion cell, comprise the following steps: one, by zinc nitrate, zinc chloride or zinc acetate zinc solution and ferric nitrate, iron chloride or ironic citrate iron salt solutions, by the ratio 1 ~ 24:8 of zinc salt with molysite amount of substance, be mixed to get iron zinc mixed solution; Two, added by organic matter pyrolysis carbon matrix precursor in iron zinc mixed solution, temperature is 50 ~ 100 DEG C, and rotating speed is 10 ~ 25r/min, stirs 30 ~ 180min, obtains even slurry; Described organic matter pyrolysis carbon matrix precursor is more than one in citric acid, glucose, phenolic resins, epoxy resin and sucrose, organic matter pyrolysis carbon matrix precursor presses the ratio of carbon atom and the amount of zinc-iron atom species, for (0 < carbon atom amount of substance≤1): (amounts of 4 zinc-iron atom species), or (amount of 1 < carbon atom amount of substance≤14:4 zinc-iron atom species); Three, by even slurry with 0.5 ~ 3 DEG C/min heating rate from room temperature to 50 ~ 200 DEG C, heat preservation solidification 5 ~ 48h, naturally cools to room temperature in stove; Four, at protective atmosphere nitrogen or argon gas; flow is under 0.9 ~ 2L/min condition; with 0.5 ~ 5 DEG C/min heating rate from room temperature to 700 ~ 900 DEG C; Isothermal sinter 14 ~ 24h; room temperature is naturally cooled in stove; obtaining composite cathode material for lithium ion cell, is the ZnO/FeO composite material that ZnO and FeO is formed, or the ZnO/FeO/C composite material of porous carbon C clading ZnO and FeO formation.
2. the preparation method of composite cathode material for lithium ion cell according to claim 1, it is characterized in that: described heat preservation solidification 5 ~ 48h, after naturally cooling to room temperature in stove, put into planetary ball mill, ball milling 2 ~ 10h, ball material mass ratio is 10 ~ 20:1, and ball material is stainless shot, diameter is 10mm, obtains the powder that average grain diameter is 10 ~ 200 μm.
3. the preparation method of composite cathode material for lithium ion cell according to claim 1, it is characterized in that: described Isothermal sinter 14 ~ 24h, after naturally cooling to room temperature in stove, put into planetary ball mill, ball milling 2 ~ 10h, ball material mass ratio is 10 ~ 20:1, and ball material is stainless shot, diameter is 10mm, and sieving through 200 orders obtains the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μm.
4. the preparation method of composite cathode material for lithium ion cell according to claim 1, is characterized in that: be that 0.1 ~ 10mol/L is dissolved in deionized water by zinc nitrate, zinc chloride or zinc acetate by zinc atom concentration, obtains zinc solution; Be that 0.1 ~ 10mol/L is dissolved in deionized water by ferric nitrate, iron chloride or ironic citrate by iron atom concentration, obtain iron salt solutions.
5. the preparation method of composite cathode material for lithium ion cell according to claim 4, it is characterized in that: described is that 0.1 ~ 10mol/L is dissolved in deionized water by zinc nitrate, zinc chloride or zinc acetate by zinc atom concentration, temperature is 25 ~ 50 DEG C, rotating speed is 10 ~ 25r/min, and the time is 30 ~ 180min; Described is that 0.1 ~ 10mol/L is dissolved in deionized water by ferric nitrate, iron chloride or ironic citrate by iron atom concentration, and temperature is 25 ~ 50 DEG C, and rotating speed is 10 ~ 25r/min, and the time is 30 ~ 180min.
6. the preparation method of composite cathode material for lithium ion cell according to claim 1, it is characterized in that: by zinc solution and iron salt solutions, be 10 ~ 50 DEG C in temperature, rotating speed is 10 ~ 25r/min, and the time is be mixed to get iron zinc mixed solution under 30 ~ 180min condition.
7. the preparation method of composite cathode material for lithium ion cell according to claim 1, it is characterized in that: when described organic matter pyrolysis carbon matrix precursor is two or more, often kind of material adds respectively, respectively under rotating speed is 10 ~ 25r/min, stirs 30 ~ 180min.
8. the preparation method of composite cathode material for lithium ion cell according to claim 1, is characterized in that: described step one, by the ratio 1.6 ~ 8:8 of zinc salt with molysite amount of substance; Described step 2, temperature is 70 ~ 100 DEG C, rotating speed is 10 ~ 15r/min, stir 30 ~ 120min, organic matter pyrolysis carbon matrix precursor presses the ratio of carbon atom and the amount of zinc-iron atom species, for (0.08 < carbon atom amount of substance≤0.96:4), or (2.12 < carbon atom amount of substance≤13.44:4); Described step 3, with 1 ~ 3 DEG C/min heating rate from room temperature to 100 ~ 150 DEG C, heat preservation solidification 5 ~ 24h; Described step 4, flow is 0.9 ~ 1.5L/min, with 0.5 ~ 4 DEG C/min heating rate from room temperature to 700 ~ 750 DEG C.
9. the preparation method of composite cathode material for lithium ion cell according to claim 8, is characterized in that: described step one, by the ratio 4:8 of zinc salt with molysite amount of substance; Described step 2, temperature is 90 DEG C, and rotating speed is 15r/min, stirs 90min, and organic matter pyrolysis carbon matrix precursor presses the ratio of carbon atom and the amount of zinc-iron atom species, is 0.8:4, or 9.92:4; Described step 3, with 2 DEG C/min heating rate from room temperature to 110 DEG C, heat preservation solidification 12h; Described step 4, flow is 1L/min, with 3 DEG C/min heating rate from room temperature to 700 DEG C, Isothermal sinter 24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210169192.XA CN102651472B (en) | 2012-05-28 | 2012-05-28 | Composite cathode material of lithium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210169192.XA CN102651472B (en) | 2012-05-28 | 2012-05-28 | Composite cathode material of lithium ion battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102651472A CN102651472A (en) | 2012-08-29 |
| CN102651472B true CN102651472B (en) | 2015-06-10 |
Family
ID=46693410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210169192.XA Active CN102651472B (en) | 2012-05-28 | 2012-05-28 | Composite cathode material of lithium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102651472B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103236519B (en) * | 2013-04-16 | 2015-05-20 | 北京科技大学 | Porous carbon base monolith composite material for lithium ion battery, and preparation method thereof |
| CN105552334B (en) * | 2016-01-11 | 2018-04-17 | 杭州电子科技大学 | A kind of preparation method of carbon film coated zinc oxide hollow ball |
| CN109647584A (en) * | 2018-12-10 | 2019-04-19 | 桂林理工大学 | A kind of sand milling method of modifying of lithium ion battery mineral negative electrode material |
| CN110371924B (en) * | 2019-07-25 | 2022-06-14 | 许昌学院 | A kind of Fe2O3 porous nanowire electrode material, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301048A (en) * | 1999-09-28 | 2001-06-27 | 三星Sdi株式会社 | Activated negative electrode materials for lithium secondary battery, electrodes, batteries and preparation of the materials |
| CN101847721A (en) * | 2010-05-19 | 2010-09-29 | 宁波职业技术学院 | Carbon-coated antimony-zinc alloy material of cathode for lithium-ion battery and method for preparing same |
| CN102208638A (en) * | 2011-04-26 | 2011-10-05 | 浙江大学 | High-capacity lithium ion battery cathode composite material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8216719B2 (en) * | 2006-02-13 | 2012-07-10 | Hitachi Maxell Energy, Ltd. | Non-aqueous secondary battery and method for producing the same |
| KR101155919B1 (en) * | 2010-08-06 | 2012-06-20 | 삼성에스디아이 주식회사 | Negative active material for rechargeable lithium battery and rechargeable lithium battery including same |
-
2012
- 2012-05-28 CN CN201210169192.XA patent/CN102651472B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301048A (en) * | 1999-09-28 | 2001-06-27 | 三星Sdi株式会社 | Activated negative electrode materials for lithium secondary battery, electrodes, batteries and preparation of the materials |
| CN101847721A (en) * | 2010-05-19 | 2010-09-29 | 宁波职业技术学院 | Carbon-coated antimony-zinc alloy material of cathode for lithium-ion battery and method for preparing same |
| CN102208638A (en) * | 2011-04-26 | 2011-10-05 | 浙江大学 | High-capacity lithium ion battery cathode composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102651472A (en) | 2012-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102790217B (en) | Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof | |
| CN103682359B (en) | Negative material and preparation method thereof, negative pole, the battery with the negative pole | |
| CN103094558B (en) | A kind of zinc ferrite based nano composite material, preparation method and its usage | |
| CN109449385B (en) | Carbon-coated amorphous silicon/graphene composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN102891299B (en) | High-rate lithium ion battery cathode material and preparation method and application thereof | |
| CN103165862B (en) | A kind of high performance lithium ionic cell cathode material and preparation method thereof | |
| CN100448772C (en) | High density ultrafine composite ferric lithium phosphate anode material and preparation method | |
| CN102569769B (en) | Preparation method for lithium titanate and graphene composite electrode materials | |
| CN102694152B (en) | A kind of negative active core-shell material and preparation method thereof and a kind of lithium ion battery | |
| CN101752562B (en) | Compound doped modified lithium ion battery anode material and preparation method thereof | |
| WO2010040285A1 (en) | Titanium-containing active material for negative electrodes and its production method and titanium-containing power lithium battery | |
| CN103972497B (en) | Lithium-ion battery Co2SnO4/C nanocomposite negative electrode material and its preparation and application | |
| CN106602024B (en) | Surface in-situ modification type lithium-rich material and preparation method thereof | |
| CN103151522A (en) | Mixed crystal form ferric fluoride cathode material and preparation method thereof | |
| CN102208644B (en) | Composite lithium manganese phosphate serving as lithium ion battery anode material and preparation method thereof and lithium ion battery | |
| CN102623705B (en) | Lithium ion battery cathode material LiFePO4/C, and preparation method and application thereof | |
| CN103151508A (en) | Lanthanum lithium titanate doped composite negative electrode material of lithium ion battery and preparation method thereof | |
| CN104241630A (en) | Lithium nickel cobalt manganate hollow sphere as well as preparation method and application thereof | |
| CN115148977A (en) | A kind of preparation method of single-atom-containing carbon material and its application in lithium-sulfur battery | |
| CN109449379A (en) | A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and the preparation method and application thereof | |
| CN105140493A (en) | Nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials and preparation method thereof | |
| CN106887575A (en) | A kind of cobalt acid zinc/graphene composite negative pole and preparation method thereof and lithium ion battery | |
| CN102651472B (en) | Composite cathode material of lithium ion battery and preparation method thereof | |
| CN106784677A (en) | A kind of preparation of lithium-enriched cathodic material of lithium ion battery and improved method | |
| CN112290022A (en) | Lithium ion battery anode lithium supplement additive and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth, Patentee after: Beitrei New Materials Group Co.,Ltd. Address before: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth, Patentee before: Shenzhen BTR New Energy Materials Inc. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230418 Address after: A2001, Building 1, Beiteri Science and Technology Park, No. 26 Baolan Road, Laokeng Community, Longtian Street, Pingshan District, Shenzhen City, Guangdong Province, 518118 Patentee after: Shenzhen beiteri New Energy Technology Research Institute Co.,Ltd. Address before: 518106 Guangdong Shenzhen Guangming New District Gongming office, saitan community high tech Industrial Park eighth Patentee before: Beitrei New Materials Group Co.,Ltd. |