CN101499522B - Anode material of lithium battery and its production method, lithium secondary battery employing the same - Google Patents
Anode material of lithium battery and its production method, lithium secondary battery employing the same Download PDFInfo
- Publication number
- CN101499522B CN101499522B CN200810006703XA CN200810006703A CN101499522B CN 101499522 B CN101499522 B CN 101499522B CN 200810006703X A CN200810006703X A CN 200810006703XA CN 200810006703 A CN200810006703 A CN 200810006703A CN 101499522 B CN101499522 B CN 101499522B
- Authority
- CN
- China
- Prior art keywords
- lithium
- porousness
- particles
- lithium oxide
- anode material
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 69
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000010405 anode material Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 66
- 239000002105 nanoparticle Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000000835 fiber Substances 0.000 claims abstract description 10
- 239000011859 microparticle Substances 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 20
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 239000004020 conductor Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000010450 olivine Substances 0.000 claims description 6
- 229910052609 olivine Inorganic materials 0.000 claims description 6
- -1 iron ion Chemical class 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000011147 inorganic material Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011368 organic material Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910013733 LiCo Inorganic materials 0.000 claims description 2
- 229910015645 LiMn Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 239000000843 powder Substances 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000010586 diagram Methods 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 10
- 239000002159 nanocrystal Substances 0.000 description 10
- 238000000840 electrochemical analysis Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000002931 mesocarbon microbead Substances 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 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
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009795 derivation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 206010036590 Premature baby Diseases 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004712 monophosphates Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Images
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)
- Secondary Cells (AREA)
Abstract
The invention relates to a lithium battery anode material, a manufacturing method thereof, an application thereof and a lithium secondary battery made of the material. The lithium battery anode material comprises a porous lithium oxide micron particle which comprises a plurality of porous lithium oxide nano particle; the inside of each porous lithium oxide nano particle is provided with a first conductive layer, a hole, a second conductive layer and conductive fiber; the hole is defined by the connection of the porous lithium oxide nano particles; the second conductive layer is coated on the surface of at least one of the porous lithium oxide nano particles and contacts with the first conductive layer to form a 3-D conductive network among the porous lithium oxide micron particles; and the conductive fiber is connected with the second conductive layer. The inside of each porous lithium oxide micron particle is provided with a plurality of nano lithium oxide particles, a nano porous channel and a nano 3-D conductive network. In addition, the conductive fiber is connected to the second conductive layer.
Description
Technical field
The present invention relates to a kind of electrode material, and particularly relates to a kind of anode electrode material that is used for lithium secondary battery.
Background technology
Lithium battery is a kind of of secondary cell (getting final product TunePower), and it is mainly formed by positive pole, liquid state organic electrolyte or the solid electrolyte of lithium alloy oxide and as the carbon material of negative pole.The application of lithium battery at present mainly is as 3C articles for use such as mobile phone, notebook computer, digital camera, video cameras, with the power supply source as the required high-energy-density of the above-mentioned 3C Product of supply.
Yet, has more high-power application for more above-mentioned 3C articles for use, for example be application such as electric motor car and hand tool, the application of lithium secondary battery is prematurity still then, its reason is that the anode electrode material of applied lithium metal oxide in the present lithium secondary battery has the low excessively problem of electrical conductivity, so when high discharging current, will meet with the problem of material internal current potential deficiency, thereby make the usability that has reduced material when the embedding/embedding of lithium ion goes out in the lithium secondary battery, and then deterioration lithium battery high electric current charging and discharging capabilities with and cycle life.
Therefore, the positive electrode that just needs a kind of electrical conductivity more to promote with the life-span and the charging and discharging capabilities of lifting lithium secondary battery, and then improves its application in the high power aspect.
Summary of the invention
The positive electrode that the object of the present invention is to provide a kind of electrical conductivity more to promote with the life-span and the charging and discharging capabilities of lifting lithium secondary battery, and then improves its application in the high power aspect.
Therefore, the invention provides the manufacture method of a kind of anode material of lithium battery, anode material of lithium battery and use the lithium secondary battery of above-mentioned anode material of lithium battery.
According to an embodiment, the invention provides a kind of anode material of lithium battery, comprising:
One porousness lithium oxide micro particles, wherein this porousness lithium oxide micro particles comprises: a plurality of porousness lithium oxide nano-particles are provided with one first conductive layer in these porousness lithium oxide nano-particles; One hole is limited and is formed in linking back institute by these porousness lithium oxide nano-particles; One second conductive layer is coated on the surface of one of these porousness lithium oxide nano-particles at least and contacts this first conductive layer, to form the 3-D conductive network in described porousness lithium oxide micro particles; And a conductive fiber, link described second conductive layer.Have a plurality of nanometer lithium oxide particles, nanoporous passage and nanometer 3-D conductive network in this porousness lithium oxide micro particles and form, have a conductive fiber outward and connect into outer second conductive layer.
According to an embodiment, the invention provides a kind of lithium secondary battery, comprising:
One positive pole comprises aforesaid anode material of lithium battery; One negative pole; And an ionic conduction layer, be folded between described positive pole and the described negative pole.
According to an embodiment, the invention provides a kind of manufacture method of two stages of anode material of lithium battery calcining, comprising:
Provide to comprise one of lithium ion predecessor, phosphate predecessor and iron ion predecessor mixed-powder, wherein this mixed-powder comprises a plurality of porousness nano particles; Mix this mixed-powder and water to form one first slurry; This first slurry of granulation calcination is to form the spherical predecessor of a first kind; Mix the spherical predecessor of this first kind, electric conducting material and water to form one second slurry; This second slurry of granulation calcination is to form a plurality of porousness lithium oxide micro particles; And mix these porousness lithium oxide micro particles, a conductive carbon material and a binding agent, to form this anode material of lithium battery.
The present invention is by using iron lithium phosphate through upgrading as positive electrode, it has more surface area, less pore size, lower resistance value and suitable electric conducting material and covers situation, thus help promoting the iron lithium phosphate structure electron conduction, improve the evolving path of lithium ion and easily make to make when being added with electrolyte solution and be full of hole and increase response area and reaction chance in order to ionic conduction and by increasing surface area.
Use in the lithium secondary battery of positive electrode of the present invention, because the porous crack conductive structure that porousness lithium metal oxide micro particles is construed as in the structure of positive electrode, thereby has a splendid electrical performance, be beneficial to high current discharge, also promptly be beneficial to high-power application, and be applicable to the application that discharges and recharges of high power value, thereby show that the iron lithium phosphate positive electrode through upgrading has the good conductive degree among the present invention, and then can easier derivation electronics and make lithium ion more easily break away from the iron lithium phosphate crystal.
For above and other objects of the present invention, feature and advantage can be become apparent, a preferred embodiment cited below particularly, and conjunction with figs. are described in detail below:
Description of drawings
Fig. 1 is a schematic diagram, has shown the section situation according to the cathode plate for lithium secondary battery structure of one embodiment of the invention;
Fig. 2 is a schematic diagram, has shown the structure according to the positive electrode of one embodiment of the invention;
Fig. 3 is a schematic diagram, has shown among Fig. 2 the structure of contained conducting particles in the positive electrode;
Fig. 4 a, 4b and 4c are a series of schematic diagrames, have shown the crystal structure according to positive electrode in one embodiment of the invention respectively;
Fig. 5 is a schematic diagram, has shown the lithium secondary battery according to one embodiment of the invention;
Fig. 6 is a schematic diagram, has shown the lithium secondary battery according to another embodiment of the present invention;
Fig. 7 is a chart, has shown the X light diffracting analysis result according to the positive electrode of one embodiment of the invention;
Fig. 8 is a chart, has shown the electrochemical analysis result according to the positive electrode of one embodiment of the invention;
Fig. 9 is a chart, has shown the electrochemical analysis result according to the positive electrode of one embodiment of the invention; And
Figure 10 is a chart, has shown the electrochemical analysis result according to the positive electrode of the present invention's one comparative example.
Wherein, primary clustering symbol description:
10～collector plate;
12～positive electrode material layer;
14～anode plate structure;
16～lithium metal oxide;
17～conductive carbon material;
18～binding agent;
20～porousness lithium oxide micro particles;
30～be coated with the porousness lithium oxide nano-particles of conductive layer;
30 '～be not coated with the porousness lithium oxide nano-particles of conductive layer;
32～conductive layer;
34～hole;
36～conductive fiber;
40～conductive layer;
50～nanocrystal;
100～column type lithium secondary battery;
102～ionic conduction layer;
104～positive pole;
106～negative pole;
108～shell;
110～positive terminal;
112～negative terminal;
200～coin type lithium secondary battery;
202～ionic conduction layer;
204～positive pole;
206～anode cover;
208～negative pole;
210～negative electrode casing;
250～gasket.
Embodiment
Please refer to the schematic diagram of Fig. 1, shown section situation according to the anode plate structure 14 of one embodiment of the invention.At this, anode plate structure 14 has comprised the positive electrode material layer of coating on the collector plate 10 12.Collector plate for example is the conductive sheet metal of aluminium (Al), aluminium/carbon (Al/C), nano aluminum/aluminium materials such as (nano-Al/Al).Mainly comprised lithium metal oxide 16, conductive carbon material 17 and binding agent (binder) 18 in positive electrode rete 12, wherein lithium metal oxide 16: conductive carbon material 17: the weight ratio of binding agent 18 is approximately between 93: 3: 4～75: 10: 15.
Please refer to the schematic diagram of Fig. 2, the signal situation that has shown porousness lithium oxide micro particles 20 contained in the lithium metal oxide 16 according to one embodiment of the invention, and lithium alloy oxide 16 mainly is to form (not showing that at this it is in conjunction with situation) by 20 granulations of a plurality of porousness lithium oxide micro particles, and its contained positive electrode particle 20 has respectively between 5 microns～20 microns average grain diameter, between 1m
2/ g～50m
2The surface area of/g and between the porosity of 0.02c.c./g～0.12c.c./g.
As shown in Figure 2, the schematic construction that has only shown a porousness lithium oxide micro particles 20 separately, it comprises a plurality of porousness lithium oxide nano-particles 30, and these porousness lithium oxide nano-particles 30 have the average grain diameter between 100 nanometers～500 nanometers respectively.
These porousness lithium oxide nano-particles 30 therebetween then limit after linking and form a plurality of holes 34, and above-mentioned hole 34 can be orderly or unordered misclosure hole and have between one of 10～30 nanometers size, in lithium secondary battery is used, providing electrolyte or moistening position and the electrochemical response area of electrolyte, and then raising ionic conduction speed.
In addition, on the surface of most porousness lithium oxide nano-particles 30, be coated with a conductive layer 32.Yet, in porousness lithium oxide micro particles 20, still have the porousness lithium oxide nano-particles that is not coated on a small quantity for conductive layer 32, be denoted as 30 ' at this.In addition, in porousness lithium oxide micro particles 20, also include several conductive fibers 36, it is to be linked to conductive layer 32 and may to protrude in the surface of porousness lithium oxide micro particles 20 and/or extend in the hole 34 between porousness lithium oxide nano-particles 30/30 ', so that link the porousness lithium oxide nano-particles 30/30 ' that is positioned at porousness lithium oxide micro particles 20 inside.The material of conductive layer 32 for example is metal, conduction organic material or conducting inorganic material materials such as (as conductive carbon), and has one of 3～10 nanometers thickness.And the material of conductive fiber 36 for example is metal, conduction organic material or conducting inorganic material materials such as (as conductive carbon), and its average diameter is about 0.5～3 micron.So, the formation by conductive layer 32 and conductive fiber 36 with may link situation, thereby can in lithium oxide micro particles 20, be construed as three-dimensional (3-D) conductive network and help the conduction of electronics.
Please refer to the signal situation of Fig. 3, it has shown among Fig. 2 the structure of contained porousness lithium oxide nano-particles in the porousness lithium oxide micro particles 20.As shown in Figure 3, be coated with a conductive layer 32 on the surface of this porousness lithium oxide nano-particles 30, this porousness lithium oxide nano-particles 30 has a plurality of hole (not shown)s, its nanocrystal 50 by a plurality of lithium metal oxides is formed, then be formed with a conductive layer 40 between these nanocrystals 50,40 contacts of conductive layer also link conductive layer 32.At this, 50 the average grain diameters of nanocrystal in the porousness lithium oxide nano-particles 30 with 10～100 nanometers.So, by formation and the binding of conductive layer 40, thereby can in lithium oxide nano-particles 30, be construed as the conduction that three-dimensional (3-D) conductive network is beneficial to electronics with conductive layer 32.
At this, the nanocrystal 50 of lithium metal oxide powder can comprise the lithium metal oxide of layer structure, spinel structure and olivine structural.Material with nanocrystal 50 of layer structure for example is LiCoO
2, LiNiO
2, LiMnO
2Or LiCo
xNi
yMn
zO
2(wherein x+y+z=1), Fig. 4 a has then illustrated the LiCoO that adopts
2The signal situation of the layer structure of material nano crystal.Material with nanocrystal 50 of spinel structure then for example is Li
2Ti
5O
8Or LiMn
2O
4, Fig. 4 b has then illustrated the LiMnO that adopts
2The signal situation of the spinel structure of material nano crystal.50 of nanocrystals with olivine structural for example are LiFePO
4/ C, LiFePO
4Or Li
xM
1-(d+t+q+r)D
dT
tQ
qR
r(XO
4), wherein M is the mixture of selecting from Fe, Mn, Co, Ti, Ni or above-mentioned material, and D is element M g, Ni, Co, Zn, Cu and the Ti that selects from divalence, and T is element al, Ti, Cr, Fe, Mn, Ga, Zn and the V that selects from trivalent, and Q is element ti, Ge, Sn and the V that selects from tetravalence, and R is element V, Nb and the Ta that selects from pentavalent, and X is the mixture of selecting from Si, S, P, V or above-mentioned material, wherein 0≤x≤1,0≤d, t, q, r≤1 and one of d, t, q and r are non-vanishing at least.Fig. 4 c has then illustrated employing LiFePO
4The signal situation of olivine structural.
Fig. 5 is a schematic diagram, shown lithium secondary battery 100 according to one embodiment of the invention, negative pole (anode) 106 and anodal (cathode) 104 that it has the column profile and is oppositely arranged, and negative pole 106 and anodal 104 is to intercept mutually for 102 on ionic conduction layer (ionic conductor).At this, negative pole 106, positive pole 104 are to be 108 coatings of shell (housing) with ionic conduction layer 102, and negative pole 106 and anodal 104 then is linked to a negative terminal (anode terminal) 112 and one positive terminal (cathodeterminal) 110 respectively.In lithium secondary battery as shown in Figure 5, anodal 104 is the positive electrode material layers 12 that adopt as shown in Figure 1, negative pole 106 then for example is carbon, graphite, carbonaceous mesophase spherules (mesocarbonmicrobeads, MCMB) or the substrate of lithium conductive material such as (Li), then include the barrier film or the gelated electrolyte that contain lithium electrolyte in the ionic conduction layer 102.At this, by adopting positive electrode material layer 12 of the present invention, lithium secondary battery 100 thereby be applicable to and need to use the product of high charge-discharge power to use.
Fig. 6 then is a schematic diagram, it has shown the lithium secondary battery 200 according to another embodiment of the present invention, it has a coin shape external form (coin shape), it has positive pole 204 that comprises the positive electrode rete and the negative pole 208 that comprises the negative material rete, and wherein negative pole 208 is storehouses and is arranged at anodal 204 top and is gripped with ionic conduction layer 202 between negative pole 208 and anodal 204.At this, negative pole 210, ionic conduction layer 202 with anodal 204 coated by anode cover 206 and coated by negative electrode casing 210 through stacking back in negative side in side of the positive electrode, anode cover 206 and negative electrode casing 210 are then respectively as negative terminal and positive terminal.At this, in one of anode cover 206 portion, then be embedded with gasket (gasket) 250, so as to avoiding the outflow of lithium secondary battery 200 contained materials.
In lithium secondary battery as shown in Figure 6, anodal 204 is the positive electrode material layers 12 that adopt as shown in Figure 1, negative pole 208 then for example is carbon, graphite, carbonaceous mesophase spherules (mesocarbon microbeads, MCMB) or the substrate of lithium conductive material such as (Li), then include the barrier film or the gelated electrolyte that contain lithium electrolyte in the ionic conduction layer 202.At this, by adopting positive electrode material layer 12 of the present invention, thereby be applicable to and need to use the product of high charge-discharge power to use.
In addition, the present invention also provides a kind of manufacture method of positive electrode, comprises the following steps:
(a) provide the powder of a lithium ion predecessor, it comprises LiOH, Li
2CO
3Or C
2H
5COOLi; The powder of monophosphate predecessor, it comprises (NH
4)
2HPO
4, NH
4H
2PO
4, H
3PO
4Or (NH
4)
3PO
4And the powder of an iron ion predecessor, it comprises Fe
2C
2O
4XH
2O, Fe, Fe
2(C
2O
4)
3Or Fe (C
2H
5COO)
2, the powder of above-mentioned predecessor comprises a plurality of porousness nano particles;
(b) powder of the above-mentioned three kinds of predecessors of mixing and water are to form one first slurry, and the mixed proportion of the powder of wherein above-mentioned three kinds of predecessors is then approximately between 1: 1: 1 (mole ratio);
(c) above-mentioned first slurry of granulation calcination is to form first kind sphere (sphere-like) predecessor;
(d) mix the spherical predecessor of the above-mentioned first kind, electric conducting material and water to form one second slurry;
(e) above-mentioned second slurry of granulation calcination is to form a plurality of porousness lithium oxide micro particles; And
(f) mix these porousness lithium oxide micro particles, a conductive powder, a binding agent, be applicable to the anode plate of lithium battery with formation.
In above-mentioned enforcement situation, in step (b) in formed first slurry ratio of predecessor powder and water between 20: 80～60: 40 (wt%), and in step (d) the spherical predecessor of the first kind in formed second slurry, the ratio of electric conducting material and water was between 46: 4: 50～40: 10: 50 (wt%), and the porousness lithium oxide micro particles in step (f), the mixed proportion of conductive powder and binding agent is then approximately between 93: 3: 4～75: 10: 15 (wt%), and after mixing, it is coated on (for example being aluminium foil) on the collecting board in above-mentioned material, to form the cathode plate for lithium secondary battery pole plate.
In addition, in above-mentioned enforcement situation, employed electric conducting material is metal, conduction organic material or conducting inorganic material materials such as (as conductive carbon) in the step (d), for example is conductive carbon powder or metal dust.
Moreover in the foregoing description, the granulation calcination program of step (c) for example is the single program of spraying thermal decomposition program or is a recombination process that comprises spray drying program and sintering program.The execution temperature of the granulation calcination program in step (c) is in carrying out under 200～400 ℃, and the execution temperature of the granulation calcination program in the step (e) is then in carrying out under 600～850 ℃.
[embodiment]
At first, the predecessor mixed-powder of 750 grams and the water of 750 grams are mixed to form one first slurry.Then via a granulation calcination program with this first slurry to form the spherical predecessor of pulverous first kind.For example be one step program that adopts spraying thermal decomposition program or the composite steps program that adds sintering for employing spray drying program in this granulation calcination program.Above-mentioned granulation section burning program is in carrying out under 250 ℃ temperature.
Then, 100 these first ball-type predecessors of gram and 6 gram electric conducting materials and 100 are restrained after the solvent forming one second slurry, and above-mentioned second slurry of granulation calcination comprises the iron lithium phosphate positive electrode of a plurality of porousness micro particles with formation under 600～850 ℃ temperature.At this, the iron lithium phosphate positive electrode is made up of similar porousness micro particles shown in Figure 1, and electric conducting material is to use conductive carbon.
With above-mentioned iron lithium phosphate positive electrode and conductive carbon material and polyvinylidene fluoride (polyvinylidene, PVDF) after 84: 7: 9 ratio of foundation is weighed, adding N-N-methyl 2-pyrrolidone N-(NMP) subsequently is slurry to be uniformly mixed into, utilizing 120 microns scraper that slurry is coated thickness is on 20 microns the aluminium foil and in through carrying out vacuum bakeout behind the heating, drying removing nmp solvent, and then forms an anode plate.
Then roll above-mentioned electrode pad and it formation diameter is about 12 centimetres coin type pole plate, and employing lithium metal is the LiPF that contains of 1M as negative pole, above-mentioned coin type pole plate as anodal and employing concentration
6, propene carbonate (PC), ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio is 3: 5: 2) solution is as electrolyte solution, and then finishes the making of coin type battery.
[comparative example]
In this comparative example, employed iron lithium phosphate positive electrode is identical with processing step and embodiment.Yet, in comparative example, only use the iron lithium phosphate positive electrode and do not add electric conducting material is arranged (so can not be formed with the 3-D conductive network), and then prepare the relatively iron lithium phosphate positive electrode of usefulness.
In this comparative example, employed lithium oxide material and technology step is identical with embodiment.Yet in comparative example, only using the iron lithium phosphate material and not adding has electric conducting material, and then prepares the relatively coin type battery of usefulness.
Please refer to the chart of Fig. 7 shown according to the X light diffracting analysis result of the positive electrode of one embodiment of the invention, shown the X light diffracting analysis result of embodiment and comparative example respectively.As shown in Figure 7, embodiment has similar X light diffracting analysis result to comparative example and difference on the intensity is only arranged, therefore confirmed that the interior iron lithium phosphate structure of embodiment and comparative example is still possessed the feature of olivine structural and behind the process program upgrading of embodiment, the crystalline phase in its structure can't be changed.
In addition, please refer to the physical characteristic analysis result of the iron lithium phosphate shown in the following table 1, shown the physical characteristic of iron lithium phosphate in embodiment and the comparative example respectively.
The real density of the iron lithium phosphate in comparative example (true density) is about 3.59g/c.c., and powder density (tap density) then is about 0.65g/c.c, and then recording carbon content by elementary analysis is 0, does not have the surface that carbon is covered in iron lithium phosphate.Adopt four-point probe to test its resistance in addition and then can't measure, this demonstration for its literature value (please refer to Solid State Ionics 176 (2005) 1801), briquetting resistance is 10
9Ω, and pole plate resistance is 1.57m Ω.The surface area of measuring its every gram by specific area (BET) method is 14.61m in addition
2/ g is that the hole of 2.06 nanometers and every gram is 0.03c.c./g and measure pore size by pore-size distribution (BJH) rule.
The real density of the iron lithium phosphate in embodiment (true density) is about 3.31g/c.c., and powder density (tap density) then is about 0.79g/c.c, and then recording carbon content by elementary analysis is 2～3%, has the surface that carbon is covered in iron lithium phosphate.Adopting four-point probe to test its resistance in addition is 0.67k Ω, and pole plate resistance is 0.67m Ω.The surface area of measuring its every gram by specific area (BET) method is 30.3m in addition
2/ g is that the aperture of 2.06 nanometers and every gram is 0.06c.c./g and measure pore size by pore-size distribution (BJH) rule.
Comparison by above-mentioned physical characteristic, can learn among the embodiment that iron lithium phosphate through upgrading has more surface area, less pore size, lower resistance value and suitable electric conducting material and covers situation, thus help promoting iron lithium phosphate structure among the embodiment electron conduction, improve the evolving path of lithium ion and easily make to make when being added with electrolyte solution and be full of hole and increase response area and reaction chance in order to ionic conduction and by increasing surface area.
Table 1: the physical characteristic of iron lithium phosphate
| Test event | Carbon content (wt%) | Powder density (g/c.c.) | Real density (g/c.c.) | Briquetting resistance (Ω) | Pole plate resistance (m Ω) | Specific area surf zone (m 2/g) | Pore-size distribution hole diameter (nm) | The total hole volume of pore-size distribution single-point (c.c/g) |
| |
2～3 | 0.79 | 3.31 | 0.67K | 0.67 | 30.3 | 2.06 | 0.06 |
| Comparative example | 0 | 0.65 | 3.59 | 2*10 9 | 1.57 | 14.61 | 2.06 | 0.03 |
Please refer to the chart of Fig. 8, then shown electrochemical analysis result, shown the charging and discharging curve figure of lithium secondary battery among the embodiment according to the positive electrode of the present invention's one comparative example.As shown in Figure 8, after earlier lithium secondary battery being discharged and recharged through 0.1C, 0.2C, 1C, 2C, 3C, 5C, 8C and 12C, at first after discharging and recharging 50 circulations of life test under the condition of 0.2C/0.2C (charge/discharge), can find that capacitance is to be maintained at about 140mAh/g.Then lithium secondary battery is discharged and recharged 50 circulations of life test under the condition of 0.5C/1C (charge/discharge), can find that capacitance can be maintained at about 132mAh/g.Then again lithium secondary battery is discharged and recharged 50 circulations of life test under the condition of 1C/3C (charge/discharge), can find that capacitance can be maintained at about 121mAh/g.Therefore, because the porous crack conductive structure that porousness lithium metal oxide micro particles is construed as in the structure of the positive electrode in the lithium secondary battery, thereby have splendid electrical performance.
Fig. 9 and Figure 10 then are a series of charts, have shown the electrochemical analysis result according to the positive electrode of one embodiment of the invention respectively, have shown the charging and discharging curve figure of embodiment and comparative example respectively.
In Fig. 9, the lithium secondary battery of embodiment is carried out discharging and recharging the first time with the speed of 0.1C, its capacitance is 152/141 (charge/discharge) mAh/g, irreversible amount (about 7.3% loss) with 11mAh/g, and its capacitance only is left 132mAh/g when 0.2C discharges, reduce 9mAh/g during only than the discharge rate of 0.1C, even capacitance also has 100mAh/g during to the discharge rate of 3C, and even during to the discharge rate of 12C capacitance also have 80mAh/g.
And in Figure 10, lithium secondary battery in the comparative example carries out discharging and recharging the first time with the speed of 0.1C, its capacitance is 155/141 (charge/discharge) mAh/g, irreversible amount (about 9% loss) with 14mAh/g, and when following of the speed of 0.2C is discharged the only remaining 118mAh/g of its capacitance, and the only remaining 17mAh/g of its capacitance when discharging under the speed when 1C.
Result with reference to Fig. 9 and Figure 10 compares, be appreciated that the iron lithium phosphate positive electrode before the electrochemical analysis result (please refer to Figure 10) who adopts the lithium secondary battery (comparative example) of made iron lithium phosphate positive electrode without method of the present invention demonstrates upgrading not is unfavorable for high current discharge, also promptly is unfavorable for high-power application.In addition, the electrochemical analysis result who then demonstrates the iron lithium phosphate positive electrode behind upgrading in the electrochemical analysis result's (please refer to Fig. 9) of the lithium secondary battery (embodiment) that adopts the made iron lithium phosphate positive electrode of method of the present invention electrochemical analysis result (please refer to Figure 10) all is better than for containing the not performance of the lithium secondary battery of upgrading iron lithium phosphate positive electrode, and be applicable to the application that discharges and recharges of high power value, thereby show that the iron lithium phosphate positive electrode through upgrading has the good conductive degree among the present invention, and then can easier derivation electronics and make lithium ion more easily break away from the iron lithium phosphate crystal.In addition, owing to be porous material, so also have high surface area, make lithium ion embed the chance raising that embedding goes out, thereby be beneficial to the carrying out of high current discharge through the iron lithium phosphate material of upgrading.
Though the present invention with preferred embodiment openly as above; right its is not in order to limit the present invention; any those skilled in the art; without departing from the spirit and scope of the present invention; when can being used for a variety of modifications and variations, so protection scope of the present invention is as the criterion when looking the accompanying Claim book person of defining.
Claims (13)
1. anode material of lithium battery comprises:
One porousness lithium oxide micro particles comprises:
A plurality of porousness lithium oxide nano-particles are provided with one first conductive layer in these porousness lithium oxide nano-particles;
One hole is limited and is formed in linking back institute by these porousness lithium oxide nano-particles;
One second conductive layer is coated on the surface of one of these porousness lithium oxide nano-particles at least and contacts described first conductive layer, to form the 3-D conductive network in described porousness lithium oxide micro particles; And
One conductive fiber, it links described second conductive layer, protrude in porousness lithium oxide micro particles the surface and/or extend within the described hole;
And described porousness lithium oxide micro particles is to be obtained by following method, comprising:
Provide to comprise one of lithium ion predecessor, phosphate predecessor and iron ion predecessor mixed-powder, wherein said mixed-powder comprises a plurality of porousness nano particles;
Mix described mixed-powder and water to form one first slurry;
Described first slurry of granulation calcination is to form the spherical predecessor of a first kind;
Mix the spherical predecessor of the described first kind, electric conducting material and water to form one second slurry;
Described second slurry of granulation calcination is to form a plurality of porousness lithium oxide micro particles.
2. anode material of lithium battery according to claim 1, wherein said porousness lithium oxide micro particles has the average grain diameter between 5～20 microns.
3. anode material of lithium battery according to claim 1, wherein said porousness lithium oxide nano-particles has the average grain diameter between 100～500 nanometers.
4. anode material of lithium battery according to claim 1, wherein said porousness lithium oxide micro particles has the porosity between 0.02c.c./g～0.12c.c./g.
5. anode material of lithium battery according to claim 1, the structure of wherein said porousness lithium oxide nano-particles is layer structure, spinel structure or olivine structural.
6. anode material of lithium battery according to claim 5, the structure of wherein said porousness lithium oxide nano-particles is a layer structure, and described porousness lithium oxide nano-particles comprises LiCo
xNi
yMn
zO
2And x+y+z=1.
7. anode material of lithium battery according to claim 5, the structure of wherein said porousness lithium oxide nano-particles is a spinel structure, and described porousness lithium oxide nano-particles comprises LiMn
2O
4Or Li
2Ti
5O
8
8. anode material of lithium battery according to claim 5, the structure of wherein said porousness lithium oxide nano-particles is an olivine structural, and described porousness lithium oxide nano-particles comprises LiFePO
4Or Li
xM
L-(d+t+q+r)D
dT
tQ
qR
r(XO
4), wherein M is the mixture of selecting from Fe, Mn, Co, Ti, Ni or above-mentioned material, and D is element M g, Ni, Co, Zn, Cu and the Ti that selects from divalence, and T is element al, Ti, Cr, Fe, Mn, Ga, Zn and the V that selects from trivalent, and Q is element ti, Ge, Sn and the V that selects from tetravalence, and R is element V, Nb and the Ta that selects from pentavalent, and X is the mixture of selecting from Si, S, P, V or above-mentioned material, wherein 0≤x≤1,0≤d, t, q, r≤1 and one of d, t, q and r are non-vanishing at least.
9. anode material of lithium battery according to claim 1, wherein said second conductive layer comprise conduction organic material or conducting inorganic material.
10. anode material of lithium battery according to claim 1, wherein said second conductive layer comprises metal.
11. anode material of lithium battery according to claim 1, wherein said second conductive layer has the thickness between 3～10 nanometers.
12. anode material of lithium battery according to claim 1, wherein said hole are orderly or unordered misclosure hole.
13. a lithium secondary battery comprises:
One positive pole comprises anode material of lithium battery according to claim 1;
One negative pole; And
One ionic conduction layer is folded between described positive pole and this negative pole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810006703XA CN101499522B (en) | 2008-01-28 | 2008-01-28 | Anode material of lithium battery and its production method, lithium secondary battery employing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810006703XA CN101499522B (en) | 2008-01-28 | 2008-01-28 | Anode material of lithium battery and its production method, lithium secondary battery employing the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011104154503A Division CN102496712A (en) | 2008-01-28 | 2008-01-28 | Fabrication method for lithium battery anode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101499522A CN101499522A (en) | 2009-08-05 |
| CN101499522B true CN101499522B (en) | 2011-12-28 |
Family
ID=40946480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810006703XA Active CN101499522B (en) | 2008-01-28 | 2008-01-28 | Anode material of lithium battery and its production method, lithium secondary battery employing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101499522B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906661B (en) * | 2010-08-11 | 2012-08-29 | 河北工业大学 | Ordered layered self-assembled nanostructured lithium iron phosphate polycrystalline powder and preparation method thereof |
| WO2012098970A1 (en) * | 2011-01-17 | 2012-07-26 | 昭栄化学工業株式会社 | Positive electrode material for lithium ion secondary batteries and method for producing same |
| JP2014512639A (en) * | 2011-03-16 | 2014-05-22 | 台湾立凱電能科技股▲ふん▼有限公司 | Cathode material having two-layer carbon coating and method for producing the same |
| US20130045423A1 (en) * | 2011-08-18 | 2013-02-21 | Hong Kong Applied Science and Technology Research Institute Company Limited | Porous conductive active composite electrode for litihium ion batteries |
| CN102439771B (en) * | 2011-08-19 | 2014-04-09 | 香港应用科技研究院有限公司 | Porous conductive active composite electrode used in lithium ion battery |
| US10682699B2 (en) * | 2015-07-15 | 2020-06-16 | Hrl Laboratories, Llc | Semi-passive control of solidification in powdered materials |
| CN107546379B (en) * | 2017-08-18 | 2020-02-28 | 宁波致良新能源有限公司 | Lithium iron manganese phosphate-ternary material composite cathode material and preparation method thereof |
| CN109659519B (en) * | 2018-11-30 | 2020-09-08 | 淮安新能源材料技术研究院 | TiO2Preparation method of nanofiber-coated lithium ion battery ternary cathode material and product |
| CN109659531A (en) * | 2018-12-17 | 2019-04-19 | 中科廊坊过程工程研究院 | A kind of nickel cobalt lithium aluminate composite positive pole and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1787259A (en) * | 2004-12-10 | 2006-06-14 | 新神户电机株式会社 | Positive electrode material for lithium secondary battery, production method thereof, and lithium secondary battery |
| CN1848493A (en) * | 2006-04-21 | 2006-10-18 | 北京工业大学 | High-power nano ball shape lithium cobaltate material and producing method thereof |
| CN101636861A (en) * | 2006-12-07 | 2010-01-27 | 福斯泰克锂公司 | The preparation method of particulate cathodic material and the material for preparing by this method |
-
2008
- 2008-01-28 CN CN200810006703XA patent/CN101499522B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1787259A (en) * | 2004-12-10 | 2006-06-14 | 新神户电机株式会社 | Positive electrode material for lithium secondary battery, production method thereof, and lithium secondary battery |
| CN1848493A (en) * | 2006-04-21 | 2006-10-18 | 北京工业大学 | High-power nano ball shape lithium cobaltate material and producing method thereof |
| CN101636861A (en) * | 2006-12-07 | 2010-01-27 | 福斯泰克锂公司 | The preparation method of particulate cathodic material and the material for preparing by this method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101499522A (en) | 2009-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5072110B2 (en) | Positive electrode material used for lithium battery | |
| KR102088491B1 (en) | Negative electrode active material for lithium secondary battery and negative electrode for lithium secondary battery comprising the same | |
| CN101499522B (en) | Anode material of lithium battery and its production method, lithium secondary battery employing the same | |
| CN113207316B (en) | Artificial graphite, secondary battery, preparation method and device | |
| CN108878892B (en) | Positive pole piece and battery | |
| CN1332461C (en) | Positive electrode active material and non-aqueous electrolyte secondary cell | |
| CN113207314A (en) | Secondary battery, device, artificial graphite and preparation method | |
| WO2020135766A1 (en) | Positive electrode active material, positive electrode plate, electrochemical energy storage apparatus, and apparatus | |
| WO2015198521A1 (en) | Positive electrode, cell, cell pack, electronic device, electric vehicle, electric storage device, and electric power system | |
| CN104937749A (en) | Positive electrode for secondary cell, method for manufacturing positive electrode for secondary cell, and whole solid secondary cell | |
| JP2012099482A (en) | Positive electrode active material for lithium secondary battery, method of manufacturing positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery, and lithium secondary battery | |
| KR20170039648A (en) | Positive-electrode active material, positive electrode, battery, battery pack, electronic device, electric vehicle, electricity storage apparatus, and power system | |
| KR102425828B1 (en) | Positive active material, positive electrode and lithium battery containing the material, method of manufacturing the material | |
| TW201526369A (en) | Lithium-manganese composite oxide, secondary battery, and electric device | |
| JP2011113783A (en) | Positive electrode active material for nonaqueous electrolyte battery, nonaqueous electrolyte battery, high-output electronic equipment, and automobile | |
| KR20220064388A (en) | Secondary battery, device, artificial graphite and manufacturing method thereof | |
| US10629904B2 (en) | Positive electrode active material, positive electrode, battery, battery pack, electronic device, electric vehicle, power storage device, and power system | |
| KR102159243B1 (en) | Cathode active material of lithium secondary battery | |
| KR20170024862A (en) | Organic-inorganic composite solid battery | |
| CN114223073A (en) | Negative active material, method of preparing the same, secondary battery, and device including the secondary battery | |
| CN114041226A (en) | Electrochemical device and electronic device comprising same | |
| KR102580235B1 (en) | Positive active material, lithium battery containing the material, and method of manufacturing the material | |
| JP2023538082A (en) | Negative electrode and secondary battery containing the same | |
| JP2021106074A (en) | Negative electrode active material | |
| KR20140040388A (en) | Method for the preparation of a lithium iron phosphate of olivine crystal structure and carbon-coated lithium iron phosphate of olivine crystal structure prepared thereby, including carbon inside |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231113 Address after: 2-3, Gongye 1st Road, Pingzhen District, Taoyuan City, Taiwan, China Patentee after: Hongchen Materials Co.,Ltd. Address before: Hsinchu County, Taiwan, China Patentee before: Industrial Technology Research Institute |