CN1618731A - Preparation method of counter opal structure liFePO4 powder - Google Patents
Preparation method of counter opal structure liFePO4 powder Download PDFInfo
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- CN1618731A CN1618731A CN 200410096700 CN200410096700A CN1618731A CN 1618731 A CN1618731 A CN 1618731A CN 200410096700 CN200410096700 CN 200410096700 CN 200410096700 A CN200410096700 A CN 200410096700A CN 1618731 A CN1618731 A CN 1618731A
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- 239000000843 powder Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000002245 particle Substances 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 21
- 239000000839 emulsion Substances 0.000 claims description 20
- 229910010710 LiFePO Inorganic materials 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical class O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 229920005439 Perspex® Polymers 0.000 abstract 1
- 229940062993 ferrous oxalate Drugs 0.000 abstract 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 abstract 1
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 239000004926 polymethyl methacrylate Substances 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 6
- 229920002994 synthetic fiber Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011022 opal Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
A process for preparing the LiFePO4 powder with reverse opal structure used as positive electrode of battery includes preparing the polylatex particles suspension A from styrene, perspex and acrylic acid and the clear solution B from bihydrated ferrous oxalate, lithium carbonate and ammonium bidydrogen phosphate, dropping B into A while stirring, ultrasonic dispersing, baking, fining, pretreating and sintering.
Description
Technical field
The invention belongs to the electrochemical material preparation field, particularly a kind of LiFePO that is usually used in a kind of counter opal structure of secondary lithium battery or power source usefulness cell positive material
4Powder preparation method.
Background technology
LiFePO
4That material has is cheap, nontoxic, nonhygroscopic, Environmental compatibility is fine, rich in mineral resources, characteristics such as capacity is higher (theoretical capacity is 170mAh/g, and energy density is 550Wh/Kg), stability is fine.It is a kind of big positive electrode material equivalent material of tool potentiality.Be with a wide range of applications and the very big market requirement.Existing several synthetic methods are arranged at present:
1) solid phase method: in Japanese Patent JP2000294238, as raw material, under inert atmosphere, calcine and obtain with Ferrox, Secondary ammonium phosphate and Quilonum Retard.In European patent EP 1193784, with Fe
3(PO
4)
2And Li
3PO
4As raw material and add hydrocarbon polymer and carry out solid phase synthesis; The synthetic powder particle is thick, and material electrochemical performance is low.
2) sol-gel method: in the CN1410349 patent, with Fe (Ac)
2, FeSO
47H
2O, Ba (Ac)
2And organic acid is a raw material; Technology is comparatively complicated, if process control is improper, introduces Ba easily
2+, Fe
3+Deng impurity.
3) reversed phase lithium inserting process: in the CN1469499 patent, normal heptane-ST80 system, the microreactor synthesis of nano FePO that utilizes micro emulsion to form
4, utilize LiI to insert lithium then.This method technical process complexity, the flow process time is longer.
4) spray-drying process: S.L.Bewlay, K.Konstantinov, G.X.Wang waits the people in document " Materials Letters, 58 (11), 2004,1788." in can obtain the material of controllable grain size, technology is simple, but is unfavorable for the improvement of material property.
5) coprecipitation method: G.Arnold, J.Garche, R.Hemmer, et al. is at " Journal ofPower Sources 2003,119-121:247." middle report, this method is introduced impurity easily, is unfavorable for the improvement of material electrochemical performance.
6) emulsion desiccating method: S.T.Myung, S.Komaba, R.Takagai, et al exists., report in " ChemistryLetters, 32 (7), 2003,566 ", this method complicated process of preparation, the flow process time is longer.
7) hydrothermal method: Yang S.F, Zavalij P.Y et al is report in " electrochemistrycommunications.3,2001,505 ", and this method is unfavorable for the improvement of material electrochemical performance.
Summary of the invention
The LiFePO that the purpose of this invention is to provide a kind of counter opal structure
4Powder preparation method.It is characterized in that: the LiFePO of counter opal structure
4The processing step of powder preparation method is as follows:
(1) preparation of poly-emulsion particle: with vinylbenzene, methyl methacrylate and vinylformic acid are starting material, according to the quality proportioning be: vinylbenzene: methyl methacrylate: vinylformic acid=(15 ~ 20,): (2 ~ 10): (1 ~ 5) carries out the suspension liquid A that letex polymerization forms the poly-emulsion particle that has good stability, dry suspension liquid under 70 ℃, and calculate its solid content.
(2) it is ferrous to take by weighing 2 oxalic acid hydrates according to mol ratio: Quilonum Retard: primary ammonium phosphate=1: 0.5: 1 is that violent stirring is to dissolving fully in 10~60% the nitric acid with being dissolved in the quality percentage composition after three kinds of material mixing; Thereby can obtain the xanchromatic settled solution B of different volumetric molar concentrations.
(3) according to LiFePO in poly-emulsion particle solid load and the B solution among the suspension liquid A
4Effective content be (1~30): measure suspension liquid A and solution B in 1 scope, dropwise solution B is splashed among the suspension liquid A under brute force stirs, ultra-sonic dispersion is 30~200 minutes afterwards, will mix also refinement of system oven dry 70 ℃ under.
(4) powder after the refinement is packed in the porcelain boat, 400 ℃ of following pre-treatment are burnt till under 550~850 ℃ then under reducing atmosphere or inert atmosphere, and are incubated 8~36 hours under firing temperature, thereby obtain the LiFePO of counter opal structure
4Material.
The invention has the beneficial effects as follows that preparation process time is short, firing temperature is low, and energy consumption is low; The polycrystalline LiFePO of preparation
4The diameter of particle narrowly distributing directly burns till at inert atmosphere or under reducing atmosphere, can obtain the LiFePO of the counter opal structure of rigid carbon coating
4Powder is handled the electronic conductivity that can improve material so need not carry out the coating in later stage; The synthetic materials counter opal structure has very big specific surface area, so can improve material lithium ion rate of migration in electrochemical process to a great extent, and the material diameter of particle is adjustable.
Description of drawings
Fig. 1 is the XRD figure spectrum of present method synthetic materials under the differing temps.
Fig. 2 is the SEM figure of poly-emulsion particle.
Fig. 3 is the SEM figure of present method synthetic materials.
Fig. 4 is the SEM figure of present method synthetic materials.
Fig. 5 is the SEM figure of present method synthetic materials.
Embodiment
The invention provides a kind of LiFePO of counter opal structure
4Powder preparation method.The processing step of its preparation method is as follows:
(1) preparation of poly-emulsion particle: with vinylbenzene, methyl methacrylate and vinylformic acid are starting material, according to the quality proportioning be: vinylbenzene: methyl methacrylate: vinylformic acid=(15~20): (2~10): (1~5) carries out the suspension liquid A that letex polymerization forms the poly-newborn microballoon that has good stability.Dry suspension liquid under 70 ℃, and calculate its solid content.
(2) it is ferrous to take by weighing 2 oxalic acid hydrates according to mol ratio: Quilonum Retard: primary ammonium phosphate=1: 0.5: 1 is in 10~60% the nitric acid with being dissolved in the quality percentage composition after three kinds of material mixing, and violent stirring to dissolving fully gets final product.Thereby can obtain the xanchromatic settled solution B of different volumetric molar concentrations.
(3) according to LiFePO in poly-emulsion particle solid load and the B solution among the suspension liquid A
4Effective content be (1~30): measure suspension liquid A and solution B in 1 scope.Dropwise solution B is splashed among the suspension liquid A under brute force stirs, ultra-sonic dispersion is 30~200 minutes afterwards.Under 70 ℃, will mix system oven dry and refinement.
(4) powder after the refinement is packed in the porcelain boat, 400 ℃ of following pre-treatment are burnt till under 550~850 ℃ then under reducing atmosphere or inert atmosphere, and are incubated 8~36 hours under firing temperature, thereby obtain the LiFePO of counter opal structure
4Material.
Below by embodiment, further illustrate outstanding feature of the present invention and marked improvement, only be the present invention is described and never limit the present invention.
Prefabricated poly-emulsion particle suspension liquid:
According to the quality proportioning be: vinylbenzene: methyl methacrylate: vinylformic acid=(15~20): (2~10): (1~5) is evenly mixed.Get 20 grams then and add 12 milliliters of distilled water, 0.5 gram NH
4HCO
3, 0.3 gram ammonium persulphate with 75 ℃ of down reactions 7.5 hours, be warming up to the suspension liquid A that reacts the poly-emulsion particle that can obtain having good stability in 0.5 hour after 90 ℃ again.Dry suspension liquid under 70 ℃, and calculate its solid content.Figure 2 shows that the SEM image of poly-emulsion particle.
Embodiment 1: it is ferrous to take by weighing 0.05 mole of 2 oxalic acid hydrate respectively, 0.05 mole of phosphoric acid ammonium dihydrogen and 0.025 mole of Quilonum Retard are inserted in the beaker of 100mL, add the 20mL deionized water and stir, dropwise add concentration and be in the nitric acid of 20% (quality percentage composition) till muddy system becomes clarification.Add deionized water then, solution is made into the solution of 0.1Mol/L.Get 50 milliliters of this solution, dropwise add among 50 milliliters of poly-emulsion particle suspension liquid A, and powerful the stirring 10 minutes.With flaxen mixed system with ultrasonic dispersing under 70 ℃, dry by the fire after 40 minutes in.Mixture porphyrize after the oven dry is also crossed 120 mesh sieves.Powder after sieving is inserted in the stove, and 400 ℃ of pre-treatment are 8 hours under nitrogen atmosphere, obtain black porosity and looseness block in 16 hours 600 ℃ of insulations then, and porphyrize obtains LiFePO
4Powder.Figure 1 shows that the XRD figure spectrum of material, 3 is the SEM figure of this material shown in the figure.
Embodiment 2: it is ferrous to take by weighing 0.05 mole of 2 oxalic acid hydrate respectively, 0.05 mole of phosphoric acid ammonium dihydrogen and 0.025 mole of Quilonum Retard are inserted in the beaker of 100mL, add the 20mL deionized water and stir, dropwise add in the nitric acid of 30% (quality percentage composition) till muddy system becomes clarification.Add deionized water then, solution is made into the solution of 0.2Mol/L.Get 50 milliliters of this solution, dropwise add among 200 milliliters of poly-emulsion particle suspension liquid A, and powerful the stirring 10 minutes.Flaxen mixed system is dried down at 70 ℃ after 40 minutes with ultrasonic dispersing.Mixture porphyrize after the oven dry is also crossed 120 mesh sieves.Powder after sieving is inserted in the atmosphere furnace under nitrogen atmosphere 400 ℃ of pre-treatment 8 hours, obtained black porosity and looseness block in 24 hours 700 ℃ of insulations then, porphyrize obtains LiFePO
4Powder.Figure 1 shows that the XRD figure spectrum of material, Figure 4 shows that the SEM figure of this material.
Embodiment 3: it is ferrous to take by weighing 0.05 mole of 2 oxalic acid hydrate respectively, 0.05 mole of phosphoric acid ammonium dihydrogen and 0.025 mole of Quilonum Retard are inserted in the beaker of 100mL, add the 20mL deionization and stir, dropwise add in the nitric acid of 60% (quality percentage composition) till muddy system becomes clarification.Add deionized water then, solution is made into the solution of 0.1Mol/L.Get 50 milliliters of this solution, dropwise add among 150 milliliters of poly-emulsion particle suspension liquid A, and powerful the stirring 10 minutes.Flaxen mixed system is dried down at 70 ℃ after 40 minutes with ultrasonic dispersing.Mixture porphyrize after the oven dry is also crossed 120 mesh sieves.Powder after sieving is inserted in the atmosphere furnace under nitrogen atmosphere 400 ℃ of pre-treatment 8 hours, obtained black porosity and looseness block in 16 hours 800 ℃ of insulations then, porphyrize obtains LiFePO
4Powder.Figure 1 shows that the XRD figure spectrum of material, Figure 5 shows that the SEM figure of this material.
In the XRD figure spectrum of above-mentioned synthetic materials shown in Figure 1, (200), (101), (210), (011), (111), (211), (301), (311), (121), (410), (401), diffraction peaks such as (022) is LiFePO
4The characteristic peak of material.
Be by the foregoing description characteristics of the present invention as can be seen:
1). with Li
+, Fe
2+And PO
4 3-Precursor insert in the space between the poly-emulsion particle particle with opal structural.
2). utilize pretreatment technology will gather the counter opal structure of emulsion particle cracking and formation and original inverted configuration.
3). that utilizes counter opal structure formation has rationally solved the little problem of lithium ion rate of migration in the material than bigger serface.
4). utilize the poly-emulsion particle carbon black that cracking forms in inertia or reducing atmosphere effectively to solve LiFePO
4The problem that the material electronics specific conductivity is low.
5) .Li
+, Fe
2+And PO
4 3-Precursor be in the space that poly-emulsion particle piles up and can effectively stop Fe in the material
2+Oxidation.
6). the material preparation process is simple, and the flow process time is of short duration, and the material productive rate is higher.
Claims (4)
- A kind of LiFePO of counter opal structure 4Powder preparation method.It is characterized in that: the LiFePO of counter opal structure 4The processing step of powder preparation method is as follows:(1) preparation of poly-emulsion particle: with vinylbenzene, methyl methacrylate and vinylformic acid are starting material, according to the quality proportioning be: vinylbenzene: methyl methacrylate: vinylformic acid=(15~20,): (2~10): (1~5) carries out the suspension liquid A that letex polymerization forms the poly-emulsion particle that has good stability, dry suspension liquid under 70 ℃, and calculate its solid content;
- (2) it is ferrous to take by weighing 2 oxalic acid hydrates according to mol ratio: Quilonum Retard: primary ammonium phosphate=1: 0.5: 1 is that violent stirring is to dissolving fully in 10~60% the nitric acid with being dissolved in the quality percentage composition after three kinds of material mixing; Thereby can obtain the xanchromatic settled solution B of different volumetric molar concentrations;
- (3) according to LiFePO in poly-emulsion particle solid load and the B solution among the suspension liquid A 4Effective content be (1~30): measure suspension liquid A and solution B in 1 scope, dropwise solution B is splashed among the suspension liquid A under brute force stirs, ultra-sonic dispersion is 30~200 minutes afterwards, will mix also refinement of system oven dry 70 ℃ under;
- (4) powder after the refinement is packed in the porcelain boat, 400 ℃ of following pre-treatment are burnt till under 550~850 ℃ then under reducing atmosphere or inert atmosphere, and are incubated 8~36 hours under firing temperature, thereby obtain the LiFePO of counter opal structure 4Material.
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Cited By (1)
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CN102460786A (en) * | 2009-06-25 | 2012-05-16 | 国立大学法人长崎大学 | Composite nano porous electrode material, process for production thereof, and lithium ion secondary battery |
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CN102460786A (en) * | 2009-06-25 | 2012-05-16 | 国立大学法人长崎大学 | Composite nano porous electrode material, process for production thereof, and lithium ion secondary battery |
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