1]This application is all the information and claims the benefit of priority based on 2017.07.10 character Korea Patent Application No. 10-2017-0086896, described in the literature of the Korea patent application is included as part of this specification.
[2]The present invention relates to a 3D pattern other erection for a lithium metal electrode, more particularly to a paste or a 3D pattern mold the polymer material into a mold which emits other lithium metal electrode as a unit electrode, the mold itself, a polymeric material with 3D pattern made relates to the other, which can put a 3D pattern engraved erection unit at the same time at the other electrode surface and balham a lithium metal electrode as the electrode unit.
BACKGROUND
[3]
The price of energy due to the depletion of fossil fuels is rising, while the amplified interest in environmental pollution becomes an indispensable factor for the demand for eco-friendly alternative energy sources, the future life and, in particular, technology development for mobile devices the demand for secondary batteries as an energy source is rapidly increasing as the demand increases.
[4]
[5]
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.
[6]
[7]
In general, secondary batteries are home coating the entire active materials to the surface of the configuration on the positive and negative electrodes, and then by interposing the separator therebetween made of an electrode assembly, a cylindrical or prismatic metal can, or inside the pouch-shaped case of the aluminum laminate sheet of attached, either primarily or impregnated with a liquid electrolyte injected into the electrode assembly, or is manufactured using a solid electrolyte.
[8]
[9]
In general the negative electrode of the lithium secondary battery can be used but carbon material such as graphite, composed of lithium metal. Lithium is used as the cathode is low with a density of 0.54g / ㎤ standard reduction potential of -3.045 V also SHE has received the most attention as an electrode material of high energy density batteries due to the very low. However, in the application of the lithium metal as the negative electrode has the following problems.
[10]
[11]
Polymer electrolytes are chemically and the activity is very high for forming a passive film by the reaction with an organic electrolyte solution, the charge and discharge the lithium metal surface, oxidation of the Li (melting, dissolution) and reduction is repeated to (precipitation, deposition) reaction is not uniform in for in the formation and growth of a passive film it is severe, depending.
[12]
[13]
In this way, not only result in a reduction in capacity during charging and discharging batteries, charge and discharge of the dendrite is (lithium dendrite) is formed in the lithium secondary battery by the lithium ions in the lithium metal surface in accordance with the charge-discharge procedure is repeated growth in needle form cycles this may shorten and, causing a safety problem such as a battery resulting in the inter-electrode short-circuit (short).
[14]
[15]
While lithium metals have about 3860mAh / g by weight per unit dose as described above, there is a continuing problem with the life of the electrolytic reaction in the battery and difficulties in commercializing because of the problem of dendritic growth of lithium in accordance with the progress.
[16]
[17]
To solve this problem, and have been developed various types of technology, it is spotlighted in recent years is an increase in surface area due to the 3D structure formation. When the forming of 3D structures maximize the electrode surface area increases the area of ​​the lithium metal in contact with the electrolyte, it is possible to inhibit the growth of Dan Dendrite through it.
[18]
[19]
In a manner generally ticking a 3D pattern on the lithium metal electrode is to the inscribed-rolling 3D pattern embossed on the roller. And a roller with a 3D pattern of engraved shape would it pass has a constant pressure over the lithium metal electrode will be carved pattern on the 3D surface of the lithium metal electrode.
[20]
[21]
1 is a schematic view illustrating how to load the 3D engraved pattern (2) on the lithium metal electrode 3 by using a 3D pattern roller 1 as a prior art. 3D pattern roller 1 and the pattern 2 of the cube shape is formed in relief on the surface, it is composed of solid material than lithium metal. The 3D pattern to the roller 1, the lithium metal electrode (3) passes over the constant pressure has a lithium metal electrode 3, the surface of the 3D pattern of the cube-shaped engraved by engraving.
[22]
[23]
However, in this case a metal material because the other case the type of the like into a pattern and the problem of need to replace the roller itself, a greater problem is commonly roller used in the rolling process will get out of a lot of weight to maintain a constant pressure, so the mold release problems of the lithium metal occurs. Lithium metal is not supported very fragile metal because it is inscribed it is easy to come out caught in the roller case to rolling with a roller of metal material, if this is to be repeated to the shape of the 3D pattern schedule, which should be cleaned periodically to the roller in order to fix it again the problem occurs.
Detailed Description of the Invention
SUMMARY
[24]
As to correct the problem, such an object of the present invention described above, when the insert inscribed different types of patterns on the surface of the lithium metal electrode chair, easy replacement of the 3D pattern, increases the release of the lithium metal replacement cycle is long, the shape of the 3D pattern is carved to always provide some other 3D patterns erection.
[25]
Another object of the present invention to provide a lithium metal electrode unit and a secondary battery using the same prepared by the process of the 3D pattern lithium metal unit with the other electrode and the erection method.
Problem solving means
[26]
According to an aspect of the invention an apparatus for punching a lithium metal electrode as the electrode unit, has a mold that matches the size of the unit electrode punching mold punch which moves up and down; Die corresponding to the punching die; Mold other day emits a lithium metal electrode located on the edge of the die punch unit electrodes; 3D, and the pattern which is located in the die and yet abut the inner part edge portion is not formed in the mold punch; The 3D pattern other erection is provided comprising a.
[27]
According to another embodiment of the invention the mold punch is at least one of the mold to the mold or to paste the 3D pattern in the mold the polymer material to a metal material made of a polymeric material in one piece.
[28]
According to a further aspect of the invention the polymeric material is any one of a polyurethane acrylate, polycarbonate, polyethylene terephthalate, polypropylene, polystyrene, polybutylene terephthalate.
[29]
According to a further aspect of the invention the depth of the 3D pattern is 10 to 100㎛.
[30]
According to a further aspect of the invention, the 3D pattern is carved into any shape of the embossed or engraved.
[31]
According to a further aspect of the invention, the 3D pattern is to have a mesh (mesh), the lamella (lamellar), embossing (embo), linear, circular, elliptical, polygonal, one of the shape of the waveform.
[32]
According to a further aspect of the invention Issues chulgi of roller-shaped for supplying a lithium metal electrode prior to punching the side of the die in a row may further include a.
[33]
According to a further aspect of the invention the step of using the 3D pattern other erection, where the lithium metal electrode in the die; Step while pressing down the punching die on the punch while the other emits engrave a 3D pattern on the lithium metal electrode surface; And a step of releasing a lithium metal electrode unit from the mold by lifting the punching die punch; a method of lithium metal electrode unit prepared containing is provided.
[34]
According to a further aspect of the invention, the lithium metal electrode unit prepared by the above method is provided.
[35]
According to a further aspect of the invention, the secondary battery including the lithium metal electrode unit is provided.
Effects of the Invention
[36]
When a lithium metal unit electrodes by 3D pattern other erection provided by the present invention as produced and in the 3D pattern replacement and cleaning, reducing cost and time in comparison with the prior art, the shape of the 3D pattern becomes always inscribed constant, punching and At the same time there is an effect that the 3D pattern is engraved improve the productivity of the lithium metal electrode.
Brief Description of the Drawings
[37]
1 is a schematic diagram showing a 3D patterning method according to the prior art.
[38]
Figure 2 is a schematic diagram showing a structure of a 3D pattern other erection according to the invention.
[39]
Figure 3 is a schematic diagram showing a lithium metal electrode unit according to the invention.
[40]
Figure 4 is a schematic view to produce a 3D pattern of the mold the polymer material according to the present invention, illustrating a process of transferring it to the lithium metal.
Best Mode for Carrying Out the Invention
[41]
Hereinafter, reference to the accompanying drawings, the present invention will be described in detail. The present invention is not limited by the following Examples. Examples according to the present invention can be modified in many different forms and the scope of the invention is not to be construed as limited to the embodiments set forth herein. Embodiments of the present invention are provided to more fully illustrate the present invention the technician skilled in the art.
[42]
[43]
, The punching die punch (10) which moves up and down with the mold for 3D pattern other erection 100 is the size of the electrode unit according to the invention as shown in Figure 2; Die 14 corresponding to the mold punch (10); The mold die edge 11 located at the edge of the punch (10) which emits other lithium metal electrode 13 in the electrode unit; And 3D patterns 12 positioned on the die 14 and the inner portion are yet not in contact blade forming part of the mold punch (10); It includes.
[44]
[45]
The punching die punch 10 shown in Figure 2 has a die edge 11 to the edge, and the 3D pattern 12 on the inside is formed, the die 14 has a mold edge 11 and 3D patterns 12 and it is formed to be engaged. Mold day 11 are illustrated as thick and pointed in Figure 2 to emphasize the other foot function, actually function is composed of a thin blade shape. Die 14 is tucked above the lithium metal electrode 13 is situated the mold punch 10 is etched down to the 3D pattern die 14 and matmulrimyeonseo lithium metal electrode 13 at the same time as the other balham the surface. Of lithium metal electrode 13 is volume chulgi (not shown) and a lithium metal electrode 13, which is actually continuously fed to the lithium metal electrode 13 is preferably continuously supplied and, Fig. 2 in order to highlight the punching function part is continuously supplied to the non-illustrated.
[46]
[47]
It is another object in the present invention that the foot has a lithium metal electrode 13, the capacitance per unit weight of approximately 3860mAh / g it is extremely useful as a negative electrode. However, loose passage and have a nature to a density of 0.54g / ㎤ for pure lithium metal has a problem of forming a Dan Dendrite reacts with the electrolyte and continuously. However, a plastic working or punching is fairly easy because the fragile nature, it is easy to inscribe patterns on a 3D surface.
[48]
[49]
The size of the lithium metal electrode unit may vary depending upon the size and capacity of the battery to be manufactured. Because of the easy processing properties it is also possible to use the electrode by bending certain level. Thus stackable, folding, stacks can be used both for folding type electrode assembly.
[50]
[51]
The punching die punch 10 is emit other lithium metal electrode 13 through the vertical motion by the unit electrodes. Up and down motion may be formed by a crank type, gravity, hydraulic, it is not limited if the method capable of applying a constant pressure moves up and down. The punching die punch (10) is an attempt to cut the die 14 lithium metal electrode 13 by applying certain pressure, coming down from top to bottom and then the lithium metal electrodes 13 are located on the lithium metal electrode 13 on the unit electrode .
[52]
[53]
Die corresponding to the die punch 10, 14 is brought to emit interlocking size and the die punch 10. The die punch to the other (10) of lithium metal electrode 13 is engaged down down. Die lithium in 14 further punching a lithium metal electrode 13, a die 14 and fed to the continuous and the punching die punch 10, the before, may comprise a chulgi (not shown) of the roller-shaped volume on the side of a metal electrode (13) is pushing the following, the two punching die punch 10 is the top punching a lithium metal electrode (13) before the rise, the punching electrode punching the unit electrodes produce a series of lithium metal unit electrodes while supplying continuously It makes it possible. Die 14 is preferably provided with a punching die punch 10 has a high strength metal material than it should be for a long time to absorb the shock of the punching die punch (10).
[54]
[55]
The die punch 10 has a mold edge which emits other day lithium metal electrode 13 in the electrode unit 11 is in position. Die edge 11 is more preferable because the glass, but may be attached to the punch as a separate structure, to be formed in the mold integrally with the simple structure and maintenance. Die punch 10 has a mold edge has a size that matches the lithium metal electrode unit 11 is located at the edge of me cut lithium metal electrode 13 to the electrode unit size. Lithium metal electrodes 13 to be supplied to have the same width as the unit electrode, if supplied in a longitudinal direction of die edge 11 is located only in the transverse direction, a lithium metal electrode 13, the width has the same length as the unit electrode If it supplied in a direction die edge 11 is located only in the longitudinal direction. If lithium metal electrode 13 is applied, without consistency with the size of the unit electrodes and in which direction the mold edge 11 is to be positioned on all sides of the punching die punch (10). When considering the productivity, the lithium metal electrode 13 to be supplied is preferably a matching unit having the electrode and the length or width direction and reduce the number of the die edge 11.
[56]
[57]
In contact with a lithium metal electrode 13 as the inner portion of the die punch 10 has a 3D pattern 12 is formed. Die 14 where the lithium metal electrode 13, the and the punching die punch 10 is descended to the bottom of the die 14 and the matmulrimyeonseo when emit other lithium metal electrode 13 in the unit electrode, and the mold punch (10) as 3D patterns 12 formed on the inside abuts the lithium metal electrode 13 is grooved pattern on the 3D surface of the lithium metal electrode 13.
[58]
[59]
3D pattern 12 is embossed or be negative, and becomes the decorated 3D patterns 12, 3D pattern of the intaglio is embossed when lithium metal electrode (13) carved on the inside of the punching die punch (10), the punching die punch (10 ) 3D pattern 12 is the negative lithium metal electrode (13) carved on the inside of, the engraved pattern of the embossed 3D. 3D pattern 12 has a mesh (mesh), the lamella (lamellar), embossing (embo), linear, circular, elliptical, polygonal, any shape of the waveform which growth Dan Dendrite to give the lithium metal electrode 13 according to the usage of the battery is prepared by using the lithium metal electrode and the suppression degree may be variously selected.
[60]
[61]
The depth of the 3D pattern 12 is preferably 10 to 100㎛. The punching die punch 10, the 3D pattern in the depth of the 3D pattern 12 as deep as the lithium metal electrode 13 is formed of, is usually from several hundred within micrometer height of the lithium metal electrode (13), engraved on 3D pattern is not preferred that if the depth is less than 10㎛ Dan Dendrite growth inhibitory effect off, and if it exceeds 100㎛ undesirable difficult workability is degraded continuously carving a pattern.
[62]
[63]
The mold punch 10 of the present invention is either one made of a 3D pattern 12 being pasted into a mold or mold the polymer material is integrally of a polymeric material in a mold of a metal material. If the die of the metal mold material edge 11 is thrust and also any metal material, the paste 3D pattern 12 is molded of a polymer material on the inside of the mold. If the mold is made of a polymeric material integrally mold edge 11 and the 3D pattern 12 it consists of a polymeric material in one piece.
[64]
[65]
In the prior art there is the rolling of the electrode by using a pattern engraved roller is 3D (1), in which case there are two problems. One is when trying to replace the pattern is put inscribed not preferable in terms of cost and time, because the need to replace the roller itself and the low productivity problem, and the other is to have a constant pressure roller used in the conventional rolling process the releasability and the lithium metal does a good problem because it uses a lot of metal material weighing. If not releasability good rolled lithium metal electrode 3, a roller is lithium metal and adhere to the roller, when the lithium metal is conducted to continue rolling to the adhering state after engraved 3D pattern is original as attached to the lithium metal varies It is shown a form of the difference. Thus, to engrave the 3D pattern of a certain type should be cleaned often and lithium metal stuck in the rollers and which leads to an increase in production costs and time.
[66]
[67]
The mold punch 10 of the present invention uses paste 3D pattern 12 is molded of a polymeric material in a mold of a metal material, if you want to change the 3D pattern 12 3D pattern 12 when only the replacement mold because the problem It can be solved. In the prior art, but costly and time-consuming because the need to replace the entire roller, 3D pattern 12 is replaced, so replacing only the 3D pattern 12 is molded of polymeric material effective to reduce costs and time in accordance with the present invention a. If the entire metal mold is made of a polymeric material it is, even when replacing the mold with a 3D pattern 12 other than the die itself, so replacement is easy replacement of an entire roller with the metal and reduce the cost.
[68]
[69]
When creating the attaching 3D pattern 12 molded of polymeric material into a mold or mold itself to the polymeric material, the better the releasability of the lithium metal electrode 13 in comparison with the prior art. Polymeric material is a polycarbonate, a polyurethane acrylate, polyethylene terephthalate, polypropylene, and may have to be used such as polystyrene, polybutylene terephthalate, especially a polyurethane acrylate, polycarbonate is due to its appropriate hardness and releasability, lithium not been broken even if the mounting and at the same time that it holds the accurate pattern etched in metal, the step of pressing on the lithium metal several times, it is preferable in that it can be reused.
[70]
[71]
If the total of polymeric materials the mold die edge 11 is also made of a polymer material, even it is fully possible other foot because they lithium metal is brought workability friable nature, as described above. 3D pattern 12 mold releasability improved does not need to be cleaned do not stick to the lithium metal well after carved 3D pattern unlike the prior art, often, engraved on the lithium metal electrode (13) 3D patterns that can be engraved to a more regular form there is an effect.
[72]
[73]
A method of forming a 3D pattern in the mold of the polymer material adhering to the mold punch of the present invention may be not particularly limited, and can of any known method such as photolithography, soft lithography. A soft lithographic method, micro contact printing, decal transfer micro-transfer method (Decal Transfer Microlithography), the light-coupling mask method, replica molding, capillary - can be exemplified such as micro-molding method, and the present invention, the process is relatively simple, easy to reproduce a multi-dimensional structure and a large amount is preferable replica molding method suitable for mass production of low cost.
[74]
[75]
Replica molding is to duplicate the original document information of using a seal made of a flexible polymer. 4, the polymer precursor 31 such as to create a 3D pattern mold of the invention and preparing the silicon master mold is 3D pattern is etched 30 desired, and polyurethane acrylate on the silicon master mold pour. If after curing the polymer produced is a polyurethane acrylate, a mold (40).
[76]
Thus attaching the produced polyurethane acrylate mold 40 to the mold punch and by placing the lithium metal 50 into the die pressing down on the punch die will be the 3D pattern transferred to the lithium metal.
[77]
It may be used to prevent contamination by moisture reactivity of the lithium metal, and to give a more reliable mold release, the polyurethane acrylate (the number nm) thin layer of such a hydrophobic material on the mold using a spin-coating technique the coating than necessary .
[78]
[79]
The present invention also provides a method for producing a lithium metal electrode unit (21) using a 3D pattern other erection 100. The method comprising: positioning a lithium metal electrode 13 to the die 14; Step while pressing down the punching mold punch 10 while on the other emits a 3D pattern engraved on the surface of the lithium metal electrode (13); And a; and the step of releasing the stamping die punches 10, the lithium metal electrode unit 21 is lifted from the mold.
[80]
[81]
The present invention is also characterized in having to provide a secondary battery including a lithium metal electrode unit 21 and the electrode unit prepared by the method of manufacturing the same. Figure 3 shows a lithium metal electrode unit 21 according to the present invention. Fig shows a close-up 3D patterns 22 on the square.
[82]
[83]
The lithium metal unit electrodes 21 is prepared according to the method Dan generation of Dendrite at the electrode surface, so becomes a 3D pattern regularly engraved than, the same size and shape than the engraved by the prior art is uniform. Haejimyeon generation of Dan Dendrite uniform the effect of the electrode life and safety are improved.
[84]
[85]
Secondary battery using the electrode is improved service life and stability of the electrodes is improved because battery life and cycle characteristics.
[86]
[87]
The present invention will be described in more detail through the following examples. However, the following examples are not intended the scope of the present invention is intended to illustrate the present invention limited by the examples.
[88]
[89]
Example 1
[90]
20㎛ × 20㎛ × 20㎛ (width × width × depth) size, the punching die of the punching metal, attaching a 3D pattern mold with the cube of the 3D pattern was prepared. The material of the 3D pattern mold was a polyurethane acrylate. Die was placed a lithium metal electrode with a thickness of over 100㎛. While pressing down the punching mold from above was punched while engrave a 3D pattern on the lithium metal electrode surface. Punching a lithium metal electrode unit and the release from the mold, to exercise while continuously supplied to a lithium metal electrode through a unwinding of the roller-shaped upper and lower side of the die to mold the other punch units emitted lithium metal electrode was prepared 10.
[91]
[92]
Example 2
[93]
The diameter of the pattern of 3D 20㎛ same lithium metal electrode unit as in Example 1 except that the attaching mold having a semi-spherical 3D pattern was prepared.
[94]
[95]
Example 3
[96]
A punching mold and a lithium metal electrode unit in the same manner as in Example 1 except that the 3D pattern is used a mold made integrally of a polyurethane acrylate was prepared.
[97]
[98]
Example 4
[99]
A punching mold and a lithium metal electrode unit in the same manner as Example 2, except that the 3D pattern is used a mold made integrally of a polyurethane acrylate was prepared.
[100]
[101]
Comparative Example 1
[102]
20㎛ × × 20㎛ was prepared the roller of metal material having a pattern of cube 3D 20㎛ (width × width × depth) size. A 3D pattern engraved on the surface by rolling the lithium metal electrode having a thickness of 100㎛ to the roller. A lithium metal electrode 3D pattern was carved into a predetermined size cut were prepared 10 units of a lithium metal electrode.
[103]
[104]
Comparative Example 2
[105]
The diameter of the semi-spherical 20㎛ the 3D pattern and the comparison, except for using a roller with that of Example 1, the same unit of lithium metal electrode was produced.
[106]
[107]
Pricing the number in the order of manufacture of manufactured lithium metal electrode unit in the above embodiments and the comparative example, by observing the electrode surface to the degree to which the 3D pattern constant shown in Table 1 below. Becomes a square or circular shape of the cross section of the 3D pattern are all etched correctly and if there is depth is not constant if O, is distorted or the depth of the square or circular constant expressed as X. In addition, if the pattern is not cut exactly inscribed jyeoteuna smoothing the outer end face of the punched electrode were separately marked with △ mark in the next O, X.
[108]
[109]
TABLE 1
Electrode unit number Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2
1 O O O O O O
2 O O O O O O
3 O O O O O O
4 O O O O O O
5 O O O O O O
6 O O O O X O
7 O O O O X O
8 O O O O X X
9 O O, △ O O X X
10 O, △ O, △ O O X X

[110]
[111]
The embodiment according to the present invention, according to Table 1, while there is no continuously while leaking the 3D pattern emitted deformation of the 3D pattern engraved other comparative examples are subsequently to the deformation of the 3D pattern engraved occurs when carving a 3D pattern Able to know.
[112]
[113]
In the above, the present invention Although the description and specific examples, the invention is not limited by this patent will be described below with the teachings of the present invention by one of ordinary skill in the art available are various changes and modifications within the equivalent scope of the claims. FIG.
[114]
Reference Numerals
[115]
1: 3D pattern roller 2: 3D pattern
[116]
3: lithium metal electrode
[117]
100: 3D patterns Get an erection
[118]
10: 11 Die Punch: Die Day
[119]
12: 3D pattern 13: lithium metal electrode
[120]
14: die
[121]
21: lithium metal electrode unit
[122]
22: 3D pattern
[123]
30: silicon master mold 31: high molecular precursor
[124]
40: polymer mold (soft mold) 50: lithium metal

Claims

[Claim 1]An apparatus for punching a lithium metal electrode as the electrode unit, the punching die has a punch die that matches the size of the electrode unit which moves up and down; Die corresponding to the punching die; Mold other day emits a lithium metal electrode located on the edge of the die punch unit electrodes; 3D, and the pattern which is located in the die and yet abut the inner part edge portion is not formed in the mold punch; 3D pattern other erection comprises a.
[Claim 2]
The method of claim 1, wherein the die punch with a 3D pattern other erection, characterized in that any one of the following to the mold or mold will paste the 3D pattern in the mold the polymer material to a metal material made of a polymeric material in one piece.
[Claim 3]
The method of claim 2 wherein said polymeric material is a polycarbonate, a polyurethane acrylate, polyethylene terephthalate, polypropylene, polystyrene, polybutylene terephthalate 3D pattern other erection, characterized in that any one of the following.
[Claim 4]
According to claim 1, 3D patterns other erection, characterized in that the depth of the 3D pattern is 10 to 100㎛.
[Claim 5]
The method of claim 1, wherein the 3D pattern is 3D pattern other erection, characterized in that is engraved with one of the shape of the embossed or engraved.
[Claim 6]
The method of claim 1, wherein the 3D pattern is a mesh (mesh), the lamella (lamellar), embossing (embo), linear, circular, elliptical, polygonal, 3D pattern other erection, characterized in that, having any shape of waveform.
[Claim 7]
The method of claim 1 wherein the volume of the roller-shaped chulgi for supplying a lithium metal electrode prior to punching the side of the die in a row; 3D pattern other erection further comprising the.
[Claim 8]
The steps of a lithium metal electrode unit manufacturing method using a 3D pattern other erectile according to claim 1, where the lithium metal electrode in the die; Step while pressing down on the punch of the punching mold while the other emits engrave a 3D pattern on the lithium metal electrode surface; And a step of releasing a lithium metal electrode unit from the mold by lifting the punching die punching; lithium metal electrode unit production method comprising: a.
[Claim 9]
The lithium metal electrode unit prepared by the method according to 8.
[Claim 10]
Secondary battery comprising a lithium metal electrode unit according to claim 9.