1]The invention selenium in secondary cell electrode slurry configured to include an electrode active material, conductive material and binder using, and more particularly, amorphous selenium nanoparticles relates to a method of manufacturing a secondary cell electrode to manufacture, including the carbon particles core (core) is selenium, the shell (shell) is a carbon selenium-step of synthesizing the carbon particles; Step of dispersing or dissolving the binder in a solvent to prepare a binder solution; Mixing to prepare a slurry for electrode electrode material containing the carbon particles and the binder solution and the electrode active material, conductive material and the selenium; The step of coating the electrode slurry on a collector; A method of manufacturing a secondary cell electrode composed of a; and forming a hollow carbon nano-particles in a coating layer by coating and drying the evaporated amorphous selenium nanoparticles.
BACKGROUND
[2]
Much research and commercialization is conducted for the lithium secondary battery having the development of technology and high energy density of the demand for energy rechargeable battery as there is increasing rapidly, in particular, secondary batteries as the demand increases and the discharge voltage for a mobile device have.
[3]
[4]
Typically in the form face of the battery in the high and the demand for prismatic secondary batteries or pouch type secondary batteries with a thin thickness can be applied to products such as a mobile phone, the material surface at high energy density, discharge voltage, the lithium ion battery of the output stability, the demand is high for a lithium secondary battery such as a lithium ion polymer battery.
[5]
[6]
Such secondary batteries, depending on the shape of it be classified as a cylindrical battery cell, a prismatic battery cell, a pouch-type battery cell or the like. Of the cylindrical secondary battery comprises a cap assembly coupled to the upper portion of the electrode assembly and the cylindrical can and accommodating the electrode assembly and the can.
[7]
[8]
In the secondary battery, an electrode assembly mounted inside the battery case is a power generation device capable of charge and discharge made of a cathode / separator / anode stacking structure. The electrode assembly includes an electrode active material slurry are sequentially stacked on a positive electrode of the coated sheet and interposed (介 在) a separator between the negative electrode wound jelly roll (Jelly-roll) type, a plurality of anode and cathode separator is interposed state stacked, and can be roughly classified the unit cells stacked in a stacking / folding type wound in a separation film of a longer length. Of the jelly roll type electrode assembly is there is widely used with high energy density per weight, yet is easy to manufacture advantages.
[9]
[10]
A jelly roll type electrode assembly may have a separator interposed between the positive electrode and the negative electrode and the two electrodes are wound in a cylindrical shape forms a jelly-roll shape, the positive electrode and the negative electrode tab from the positive and negative electrodes are drawn out respectively. Conventional positive electrode tab upward, the negative electrode tab are drawn out downward.
[11]
[12]
The can is a container of a metal having a shape of substantially cylindrical in the cylindrical secondary battery, formed by machining method such as deep drawing (deep drawing). Thus, the can itself, it is also possible to perform the terminal role.
[13]
[14]
The cap assembly to the safety vent, a specific part that blocks the top of the cap, the current when the PTC device, the pressure rise in the battery, which increases when the internal battery temperature rise cell resistance significantly by blocking current to form a positive electrode terminal or the exhaust gas except the cap plate with a safety vent is a gasket, and a positive terminal connected to the positive electrode to electrically disconnect the connection from the cap plate has a structure which is sequentially laminated.
[15]
[16]
The anode of the electrode assembly is a part and the electrical connection of the cap assembly through a positive electrode tab pulled out upward, the negative electrode is bonded to the bottom surface of the can through a negative electrode tabs drawn out downward. Of course, it may be designed to change the polarity.
[17]
[18]
Further, an insulating member is located for isolation of the two, between the electrode assembly and the cap assembly, and between the bottom surface of the electrode assembly and the can, the insulating member and for isolation of the two positions.
[19]
[20]
On the other hand, the lithium secondary battery is composed of a negative electrode and a porous separator comprising an anode and a carbon-based active material comprising a lithium transition metal oxide as an electrode active material, the positive electrode is prepared by lithium transition coating a positive electrode slurry containing a metal oxide on an aluminum foil and, the negative electrode is prepared by coating a negative electrode slurry including a carbon-based active material on copper foil.
[21]
[22]
The positive electrode slurry and negative electrode slurry, the conductive material may be added to improve the electric conductivity of the active material. In particular, lithium-transition metal oxides used as positive electrode active material is therefore essentially the electrical conductivity is low, the positive electrode slurry, the conductive material is essentially added.
[23]
[24]
Such conductive material, and a carbon-based material generally used, such as carbon black, graphite, such as carbon black, acetylene black, channel black, furnace black, lamp black, thermal black, such as natural graphite or artificial graphite, and some conductive fibers such as carbon fibers or metal fibers are used in. Specific examples member challenge on the market are such as acetylene black series of Chevron Chemical Company (Chevron Chemical Company) or Denka black (Denka Singapore Private Limited), Gulf Oil Company (Gulf Oil Company) product, Vulcan (Vulcan) XC-72 (caviar boats such as CO (Cabot company) products) and Super (Super) P (Timcal Inc.).
[25]
[26]
With an increase in electricity demand and long life batteries also gradually it emerged as an electrode that can withstand long-term cycle. For long-life battery and is considered as one cause of degradation of lithium ion moves mediator in the electrolyte shortage, which result has a problem that the cycle life degradation.
[27]
[28]
In addition, the air gap within the electrolyte only with the initial electrolyte solution is injected is not fully transmitted, This can decrease the long-cycle performance with a localized reaction in the electrode. It requires that in order to increase the energy density of the battery by reducing the amount within the conductive material electrodes connecting between the minimum amount of the electrode active material and current collector, yet one simple conductive material amount of reducing not easy to keep the same battery performance, a conductive material amounts give an electrode form that can be the same performance is required.
Detailed Description of the Invention
SUMMARY
[29]
The present invention to solve the above problems is an electrode active material for making conventional electrode slurry, the conducting agent, the selenium in the mixing process of the binder is when to put mixture as the carbon particles after the electrode slurry is coated dried selenium nanoparticles are vaporized It proposes a method for producing a hollow electrode formed of a carbon nano-particles in a coating layer.
Problem solving means
[30]
According to one embodiment of the present invention by the manufacturing method of the secondary battery electrode is dispersed or dissolved in a binder in a solvent to prepare a binder solution; Mixing to prepare a slurry for electrode electrode material containing the carbon particles and the binder solution and the electrode active material, conductive material and selenium; The step of coating the electrode slurry on a collector; And while drying the coated selenium-evaporated amorphous selenium nanoparticles of carbon particles forming the hollow carbon nanoparticles in the coating layer; comprises a.
[31]
[32]
In accordance with another embodiment of the present invention, the selenium-carbon particles, the core (core) is to selenium, a shell (shell) has a carbon structure, synthesized by the self-assembly of amorphous selenium nanoparticles and carbon nanoparticles.
[33]
[34]
According to a further embodiment of the present invention, the amorphous selenium nanoparticles is vaporized at 90 to 110 ℃.
[35]
[36]
According to a further embodiment the size of the hollow carbon nano particles of the present invention is from 30 to 300nm.
[37]
[38]
According to a further embodiment of the present invention is a secondary cell electrode produced by the above method is provided.
[39]
[40]
According to a further embodiment of the present invention is a secondary battery including the electrode is provided.
[41]
[42]
According to a further embodiment of the invention it said cell is composed of any one selected from a lithium ion battery, a lithium polymer battery, a lithium ion polymer battery.
[43]
[44]
According to a further embodiment of the present invention, the battery pack comprising one or more of the secondary battery is provided.
[45]
[46]
According to a further embodiment of the present invention is a device including the battery pack as a power source is provided.
[47]
[48]
According to a further embodiment of the invention the device is mobile phone, portable computer, a smart phone, a smart pad, a netbook, a wearable electronic device, LEV (Light Electronic Vehicle), electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicle, and it is composed of any one selected from a power storage device.
Effects of the Invention
[49]
The method of producing a secondary battery electrode having a hollow carbon nano-particles is provided. Step of the manufacturing method of the secondary battery electrode by dispersing or dissolving the binder in a solvent to prepare a binder solution; Mixing to prepare a slurry for electrode electrode material containing the carbon particles and the binder solution and the electrode active material, conductive material and selenium; The step of coating the electrode slurry on a collector; And while drying the coated selenium-evaporated amorphous selenium nanoparticles of carbon particles forming the hollow carbon nanoparticles in the coating layer; comprises a.
[50]
[51]
In another aspect, the present invention provides a device using the battery pack, the battery pack using a suitable electrode, the secondary battery, a secondary battery, comprising the electrode for a long life in the same manner as described above.
Brief Description of the Drawings
[52]
1 is an illustration showing the formation of an electrode structure according to an embodiment of the present invention.
Best Mode for Carrying Out the Invention
[53]
It will be described in detail below, the preferred embodiment of the present invention. In this embodiment, not intended to limit the scope of the present invention, will presented to be illustrative only, it may be variously modified within the scope not departing from the technical gist.
[54]
[55]
Method of producing a secondary battery electrode of the present invention includes a binder dissolved or dispersed in a solvent to prepare a binder solution; Mixing to prepare a slurry for electrode electrode material containing the carbon particles and the binder solution and the electrode active material, conductive material and selenium; The step of coating the electrode slurry on a collector; And while drying the coated selenium-evaporated amorphous selenium nanoparticles of carbon particles forming the hollow carbon nanoparticles in the coating layer; comprises a.
[56]
[57]
Will be described with a secondary battery according to the present invention is less than about the binder, electrode active material, conductive material type.
[58]
[59]
Selenium of the present invention are carbon particles, selenium core, the shell is combined with carbon in the form. Core-shell structure are generally depend on self-granulation method, it is necessary to design the carbon to form the self-assembly. It may be used in the present invention, the magnetic assembly carbon commercially available and are not limited to their kind.
[60]
[61]
Binder, electrode active material, conductive material and selenium - a mixture of carbon particles together to create an electrode slurry is coated on the whole it home. Will be described with a secondary battery according to the present invention is less than about the thickness of the coating.
[62]
[63]
If the coated electrode slurry was dried at 90 to 110 ℃ is formed with a hollow carbon nanoparticles and evaporated amorphous selenium nanoparticles. Being hollow carbon nanoparticles formed means that a space remains drained while vaporizing the amorphous selenium nanoparticles. Conventional selenium does not increase the melting point vaporized at a temperature of 90 to 110 ℃, if amorphous selenium nanoparticles may consist of more disordered particles than the crystalline nano-particles, and thus from 90 to 110 ℃ because the intermolecular force is also weakened state It can be gasified at a temperature.
[64]
[65]
At a temperature of less than 90 ℃ in and is hard to be amorphous selenium nanoparticles are vaporized problem, a temperature exceeding 110 ℃ by a chance other composition in the electrode slurry is not preferable because the electrode structure can be varied.
[66]
[67]
The size of the hollow carbon nano-particles are from 30 to 300nm. Hollow carbon of less than 30nm can not reduce the amount of conductive material is a hollow carbon of more than 300nm is not preferable because it increases the porosity rather to get a reduction in the energy density.
[68]
[69]
Secondary cell electrode of the present invention produced in the same manner as described above, and is a hollow carbon nanoparticles can prevent the electrolyte shortage in the reservoir act as the electrolyte solution, it is suitable for long-life electrodes because the glass even in the electrolytic solution was impregnated. Also Reduce the amount of conductive material, yet has a high energy density advantages.
[70]
[71]
On the other hand, the present invention has the characteristic that even in providing a secondary battery comprising an electrode suitable for a long life produced in the same manner as described above.
[72]
[73]
A secondary battery according to the present invention is composed by two separate electrodes of different polarities are stacked in a separate state to the separator housing a formed electrode assembly, the electrode assembly is a cathode including a positive electrode, a negative electrode active material comprising a positive electrode active material , and it is composed of a separator.
[74]
[75]
Specifically, the positive electrode is, for example, be prepared by drying after applying the mixture of the positive electrode active material, conductive material and a binder on a positive electrode collector, as necessary, a filler may be further added to the mixture.
[76]
[77]
The positive electrode active material according to the present invention lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ) the compound substituted by a layered compound or one or more transition metals, and the like; Formula Li 1 + x Mn 2-x O 4 (where, x is from 0 to 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2, lithium manganese oxide (LiMnO of 2 ); Lithium copper oxide (Li 2 CuO 2 ); LiV 3 O 8 , LiFe 3 O 4 , V 2 O 5 , Cu 2 V 2 O 7 of vanadium oxide and the like; Formula LiNi 1-x M x O 2 (where, M = Co, Mn, Al , Cu, Fe, Mg, B or Ga, and, x = 0.01 ~ 0.3 Im) Ni-site type lithium nickel oxide (lithiated nickel expressed in oxide); Formula LiMn 2-x M x O 2 (where, M = Co, Ni, Fe , Cr, and Zn, or Ta, x = 0.01 ~ 0.1 Im) or Li 2 Mn 3 MO 8 (where, M = Fe, Co, Ni, lithium manganese composite oxides represented by Cu or Zn); A lithium portion of the formula is substituted with alkaline earth metal ions LiMn 2 O 4 ; Disulfide compounds; Fe 2 (MoO 4 ) 3 Or it may be mixed with the compound containing as a main component a lithium adsorbent material (lithiumintercalation material), such as composite oxides formed by combination thereof.
[78]
[79]
The cathode current collector is generally fabricated to have a thickness of 3 to 500 ㎛. The cathode current collector, if it has suitable conductivity without causing chemical changes in the fabricated battery is not particularly limited, for example, the surface of stainless steel, aluminum, nickel, titanium, sintered carbon, or aluminum or stainless steel on carbon, nickel, titanium and the like may be used as a surface treatment or the like. Current collector may increase the adhesive strength of the positive electrode active material to form fine irregularities on the surface thereof, films, sheets, foils, nets, porous structures, foams and non-woven fabrics and so on can take various forms.
[80]
[81]
The conductive material is commonly added in the mixture including the cathode active material to the total weight of 1 to 50% by weight. This conductive material so long as it has suitable conductivity without causing chemical changes in the fabricated battery is not particularly limited, for example, graphite such as natural graphite or artificial graphite; Carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, carbon black and thermal black; Conductive fibers such as carbon fibers and metallic fibers; Metal such as carbon fluoride, aluminum, nickel powder, powder; Conductive whiskers such as zinc oxide and potassium titanate; Conductive oxides such as titanium oxide; Poly is a conductive material such as phenylene derivative may be used.
[82]
[83]
The binder is a component assisting in binding to the total binding and the home, such as the active material and the conductive material is commonly added in the total mixture weight, includes the cathode active material of 1 to 50% by weight. Examples of the binder include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose by Woods (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinyl pyrrolidone, ethylene, polyethylene tetrafluoroethylene , polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene beuti butylene rubber, fluoro rubber and various copolymers and the like.
[84]
[85]
The filler is selectively used as a component of suppressing the expansion of the positive electrode, if the standing fibrous materials without causing chemical changes in the fabricated battery is not particularly limited, for example, up pingye polymers such as polyethylene and polypropylene; And fibrous materials such as glass fiber and carbon fiber.
[86]
[87]
Further, the cathode is fabricated by applying and drying a negative electrode material on a negative electrode current collector and, if necessary, may be further included to the same components described above.
[88]
[89]
The anode current collector is generally fabricated to have a thickness of 3 to 500 ㎛. The anode current collector, so long as it has suitable conductivity without causing chemical changes in the fabricated battery is not particularly limited, for example, of copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel surface to be surface-treated with carbon, nickel, titanium or silver, and aluminum-cadmium alloys. Also Similar to the cathode current collector, to form fine irregularities on the surface may enhance the bonding strength between the negative electrode active material, films, sheets, foils, nets, porous structures, foams and non-woven fabrics or the like can be used in various forms.
[90]
[91]
The cathode material comprises amorphous carbon or amorphous carbon, specifically I carbon such as graphitized carbon, graphite-based carbon; Li x Fe 2 O 3 (0≤x≤1), Li x WO 2 (0≤x≤1), Sn x Me 1-x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me' : Al, B, P, Si, Group 1 of the Periodic Table, Group 2, Group 3 element, a halogen; a metal composite oxide, such as 1≤z≤8); 0
[116]
Through the self-assembly of amorphous selenium, selenium nanoparticles and carbon nanoparticles were produced carbon particles. Lithium-nickel-manganese-cobalt-based active material mixture-dispersion water storage MOOH (M = Ni as a transition metal precursor for the production of 4/15 (Mn 1/2 Ni 1/2 ) 8/15 Co 0.2 use), and the mixture arithmetic cargo Li 2 Co 3 for stoichiometric ratios and mixed with (Li:: M 1.02 1) , and the mixture was mixed to prepare a lithium transition metal oxide by sintering for 10 hours at 900 ℃ in air. The lithium mixed transition metal compound and the Li 2 CoO 220: 80 positive electrode active material is 95.1 wt.% And a mean particle diameter of 35 nm and DBP absorption value of 360 ml / 100g of porous conductive material, 0.9% of polyvinylidene fluoride as a binder to the weight (polyvinylidene fluoride, PVdF) mixed with 2% by weight and then mixed to prepare a positive electrode material mixture, it 80nm selenium-by the addition of 2% by weight of carbon particles and NMP (N-methlypyrrolidone) to prepare a positive electrode material mixture slurry. After coating the positive electrode material mixture slurry on a metal current collector such as aluminum foil, a positive electrode was prepared by drying for 2 hours or more in a vacuum oven at 100 ℃.
[117]
[118]

[119]
Was and will produce a positive electrode in the same manner as in Example 1 except that the carbon particles - 150nm selenium.
[120]
[121]

[122]
250nm selenium-, except that the carbon particles to prepare a positive electrode in the same manner as in Example 1.
[123]
[124]

[125]
150nm selenium-use carbon particles, was prepared and the anode in the same way as in Example 1 except that the drying at 90 ℃.
[126]
[127]

[128]
150nm selenium-use carbon particles, was prepared and the positive electrode in the same manner as in Example 1 except for drying at 110 ℃.
[129]
[130]
[131]

[132]
Selenium-except that did not use carbon particles to prepare a positive electrode in the same manner as in Example 1.
[133]
[134]
Example 1 to 5 and Comparative Examples 1 to measure the electrolyte impregnation rate of each of the prepared positive electrode in Table 1 shows the results of the tests.
[135]
[136]
TABLE 1
Electrolyte impregnation rate (mm 3 / sec)
Example 1 1.4
Example 2 1.5
Example 3 1.6
Example 4 1.4
Example 5 1.5
Comparative Example 1 0.7

[137]
[138]
The table as shown in one of selenium in accordance with the present invention the anode of the embodiments a mixture of carbon particles prepared the positive electrode slurry was prepared by using this, Examples 1 to 5 than the positive electrode of Comparative Example 1 prepared using the conventional method the electrolytic solution impregnated speed it can be seen that twice as high.
[139]
[140]
In the above, the present invention has been been described by exemplary embodiments and drawings, the invention is not limited thereto under the technical scope of the present invention by one of ordinary skill in the art various modifications and variations within the equivalent scope of the claims to be described are possible, of course.

Claims

[Claim 1]Step of dispersing or dissolving the binder in a solvent to prepare a binder solution; Mixing to prepare a slurry for electrode electrode material containing the carbon particles and the binder solution and the electrode active material, conductive material and selenium; The step of coating the electrode slurry on a collector; Method of producing a secondary battery electrode which comprises a; evaporated amorphous selenium nanoparticles of carbon particles forming the hollow carbon nanoparticles in the coating layer - and while drying the coated selenium
[Claim 2]
The method of claim 1, wherein the selenium-carbon particles, the core (core) is selenium, the shell (shell) has a carbon structure, characterized in that synthesis using the self-assembly of amorphous selenium nanoparticles and carbon nanoparticles method of producing a secondary battery electrode.
[Claim 3]
The method of claim 1, wherein the amorphous selenium nanoparticles method of producing a secondary battery electrode characterized in that the evaporation at 90 to 110 ℃
[Claim 4]
The method of claim 1, wherein the method of manufacturing the secondary cell electrode, characterized in that the size of 30 to 300nm of the hollow carbon nanoparticles
[Claim 5]
Any one of claims 1 to a secondary cell electrode produced by the method according to any one of claim 4, wherein
[Claim 6]
The secondary battery comprising the electrode according to 5, wherein
[Claim 7]
The method of claim 6, wherein the battery is a lithium ion battery, a lithium polymer battery, a secondary battery of any one selected from the group consisting of a lithium ion polymer battery wherein
[Claim 8]
The battery pack for a secondary battery according to 7 characterized in that it comprises one or more
[Claim 9]
Device comprising the battery pack according to claim 8, wherein the power source
[Claim 10]
10. The method of claim 9, wherein the device is a mobile phone, portable computer, a smart phone, a smart pad, a netbook, a wearable electronic device, LEV (Light Electronic Vehicle), electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, and electric power storage device, characterized in that any one of selected from a device.