MIXED-ANION SOLID ELECTROLYTE AND PREPARATION METHOD AND USE THEREOF

Abstract

The invention relates to a mixed-anion solid electrolyte, having the following chemical formula: Li.sub.dAl.sub.1cY.sub.cCl.sub.3aX.sub.b, wherein Y is selected from at least one of Si.sup.4+, Ge.sup.4+, Sn.sup.4+, Sb.sup.5+, Nb.sup.5+, Ta.sup.5+, Mo.sup.6+, and W.sup.6+, and X is selected from at least one of O.sup.2, S.sup.2, F.sup., Br.sup., I.sup., and BH.sup.4; and wherein 0<d2, 0<b2, 0<a2, 0<c<0.75 and charge balance is reached.

Claims

1. A mixed-anion solid electrolyte, having the following chemical formula: Li.sub.dAl.sub.1cY.sub.cCl.sub.3aX.sub.b, wherein Y is selected from at least one of Si.sup.4+, Ge.sup.4+, Sn.sup.4+, Sb.sup.5+, Nb.sup.5+, Ta.sup.5+, Mo.sup.6+, and W.sup.6+, and X is selected from at least one of O.sup.2, S.sup.2, F.sup., Br.sup., I.sup., and BH.sup.4; and wherein 0<d2, 0<b2, 0<a2, 0<c<0.75 and charge balance is reached.

2. The mixed-anion solid electrolyte according to claim 1, wherein the Y is selected from one of Si.sup.4+, Ge.sup.4+, Sn.sup.4+, Sb.sup.5+, Nb.sup.5+, Ta.sup.5+, Mo.sup.6+, and W.sup.6+.

3. The mixed-anion solid electrolyte according to claim 2, wherein the X is selected from one of O.sup.2, S.sup.2, F.sup., Br.sup., I.sup., and BH.sup.4.

4. The mixed-anion solid electrolyte according to claim 3, wherein the chemical formula of the mixed-anion solid electrolyte is one of Li.sub.0.8AlCl.sub.2.2O.sub.0.8, LiAlCl.sub.2S.sub.0.5O.sub.0.5, Li.sub.0.8AlCl.sub.1.8O.sub.0.8Br.sub.0.4, Li.sub.0.8AlCl.sub.1.8O.sub.0.8(BH.sub.4).sub.0.4, Li.sub.0.8AlCl.sub.1.8O.sub.0.8F.sub.0.4, Li.sub.0.8Al.sub.0.9Nb.sub.0.1Cl.sub.2O, Li.sub.0.8Al.sub.0.9Ta.sub.0.1Cl.sub.2O, Li.sub.0.7Al.sub.0.9Mo.sub.0.1Cl.sub.2O, Li.sub.0.7Al.sub.0.9W.sub.0.1Cl.sub.2O, Li.sub.0.8Al.sub.0.6Si.sub.0.4Cl.sub.2.2O, Li.sub.0.9Al.sub.0.9Ge.sub.0.1Cl.sub.2O, and Li.sub.0.8Al.sub.0.6Nb.sub.0.2Ta.sub.0.2Cl.sub.2.2O.sub.1.2.

5. A preparation method of the mixed-anion solid electrolyte according to claim 1, comprising the following steps: in an inert atmosphere, mixing LiCl or LiOH, AlCl.sub.3, a lithium compound containing an X element, an aluminum compound containing an X element, and a chloride of an Y element according to a stoichiometric ratio, and then well grinding the raw materials until no granules are observed; then, performing high-temperature reaction and cooling the reaction product to obtain the mixed-anion solid electrolyte.

6. The preparation method of the mixed-anion solid electrolyte according to claim 5, wherein a temperature rise rate of the high-temperature reaction is within a range of 1 C./min to 5 C./min.

7. The preparation method of the mixed-anion solid electrolyte according to claim 5, wherein a reaction temperature of the high-temperature reaction is within a range of 150 C. to 400 C.

8. The preparation method of the mixed-anion solid electrolyte according to claim 5, wherein a reaction time of the high-temperature reaction is within a range of 0.1 h to 2 h.

9. An use of the mixed-anion solid electrolyte according to claim 1 in a preparation of a lithium-ion battery.

10. An use of the mixed-anion solid electrolyte prepared by the preparation method according to claim 5 in a preparation of a lithium-ion battery.

11. An all-solid-state lithium-ion battery, comprising a solid electrolyte, wherein the solid electrolyte is the mixed-anion solid electrolyte according to claim 1.

12. An all-solid-state lithium-ion battery, comprising a solid electrolyte, wherein the solid electrolyte is the mixed-anion solid electrolyte prepared by the preparation method according to claim 5.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0032] FIG. 1 is an impedance diagram of mixed-anion solid electrolytes of Examples 1-2, 6, 10, and 12 of the invention.

[0033] FIG. 2 shows NMR spectra of Li.sub.0.8AlCl.sub.2.2O.sub.0.8 of Example 1 of the invention and LiAlCl.sub.4 of Comparative Example 2.

[0034] FIG. 3 is an XRD pattern of the mixed-anionic solid electrolytes in FIG. 1.

[0035] FIG. 4 is a schematic diagram of the electrical conductivity of different cation doped samples.

[0036] FIG. 5 shows cyclic voltammetry curves of the lithium-ion halide solid electrolyte Li.sub.0.8AlCl.sub.2.2O.sub.0.8 in Example 1 of the invention.

[0037] FIG. 6 is a schematic diagram of a LACO+LCO/LACO/LPSC/LiIn all-solid-state battery assembled in a test example of the invention.

[0038] FIG. 7 shows cycling performance test results of the LACO+LCO/LACO/LPSC/LiIn all-solid-state battery in FIG. 6.

DESCRIPTION OF THE EMBODIMENTS

[0039] The technical solutions in the embodiments of the invention will be described clearly and completely below in connection with the drawings in the embodiments of the invention, and it will be apparent that the embodiments described here are only some, but not all of the embodiments of the invention. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the invention without creative efforts shall fall within the scope of the invention.

Example 1

[0040] This embodiment provides a mixed-anion solid electrolyte, having a chemical formula of Li.sub.0.8AlCl.sub.2.2O.sub.0.8, and its preparation method comprises the following steps.

[0041] In an argon-filled glove box with a water and oxygen content of less than 0.1 ppm, LiOH and AlCl.sub.3, with a molar ratio of 0.8:1, were ground manually in a mortar for about 10 min until LiOH and AlCl.sub.3 were well mixed and no granules were observed. The mixture was transferred to a quartz tube and sealed. The mixture was then heated to 200 C. at a temperature rise rate of 5 C./min and held at this temperature for 2 h to obtain Li.sub.0.8AlCl.sub.2.2O.sub.0.8.

Example 2

[0042] This embodiment provides a mixed-anion solid electrolyte, having a chemical formula of Li.sub.0.8AlCl.sub.1.8O.sub.0.8Br.sub.0.4, and its preparation method comprises the following steps.

[0043] In an argon-filled glove box with a water and oxygen content of less than 0.1 ppm, LiOH, AlCl.sub.3 and AlBr.sub.3, with a molar ratio of 4:3:2, were ground manually in a mortar for about 10 min until LiOH, AlCl.sub.3 and AlBr.sub.3 were well mixed and no granules were observed. The mixture was transferred to a quartz tube and sealed. The mixture was then heated to 200 C. at a temperature rise rate of 5 C./min and held at this temperature for 1 h to obtain Li.sub.0.8AlCl.sub.1.8O.sub.0.8Br.sub.0.4.

Example 3

[0044] This embodiment provides a mixed-anion solid electrolyte, having a chemical formula of Li.sub.0.8AlCl.sub.1.8O.sub.0.8(BH.sub.4).sub.0.4, and its preparation method comprises the following steps.

[0045] In an argon-filled glove box with a water and oxygen content of less than 0.1 ppm, LiOH, LiBH.sub.4, AlCl.sub.3 and Al(OH).sub.3, with a molar ratio of 6:6:13:2, were ground manually in a mortar for about 10 min until LiOH, LiBH.sub.4, AlCl.sub.3 and Al(OH).sub.3 were well mixed and no granules were observed. The mixture was transferred to a quartz tube and sealed. The mixture was then heated to 200 C. at a temperature rise rate of 5 C./min and held at this temperature for 2 h to obtain Li.sub.0.8AlCl.sub.1.8O.sub.0.8(BH.sub.4).sub.0.4.

Example 4

[0046] This embodiment provides a mixed-anion solid electrolyte, having a chemical formula of LiAlCl.sub.2S.sub.0.5O.sub.0.5, and its preparation method comprises the following steps.

[0047] In an argon-filled glove box with a water and oxygen content of less than 0.1 ppm, Li.sub.2S, AlCl.sub.3 and Al(OH).sub.3, with a molar ratio of 3:5:1, were ground manually in a mortar for about 10 min until LiOH and AlCl.sub.3 were well mixed and no granules were observed. The mixture was transferred to a quartz tube and sealed. The mixture was then heated to 200 C. at a temperature rise rate of 5 C./min and held at this temperature for 2 h to obtain LiAlCl.sub.2S.sub.0.5O.sub.0.5.

Example 5

[0048] This embodiment provides a mixed-anion solid electrolyte, having a chemical formula of Li.sub.0.8AlCl.sub.1.8O.sub.0.8F.sub.0.4, and its preparation method comprises the following steps.

[0049] In an argon-filled glove box with a water and oxygen content of less than 0.1 ppm, LiOH, AlCl.sub.3 and AlF.sub.3, with a molar ratio of 12:13:2, were ground manually in a mortar for about 10 min until LiOH, AlCl.sub.3 and AlF.sub.3 were well mixed and no granules were observed. The mixture was transferred to a quartz tube and sealed. The mixture was then heated to 200 C. at a temperature rise rate of 5 C./min and held at this temperature for 2 h to obtain Li.sub.0.8AlCl.sub.1.8O.sub.0.8F.sub.0.4.

Example 6

[0050] This embodiment provides a mixed-anion solid electrolyte, having a chemical formula of Li.sub.0.8Al.sub.0.9Nb.sub.0.1Cl.sub.2O, and its preparation method comprises the following steps.

[0051] In an argon-filled glove box with a water and oxygen content of less than 0.1 ppm, LiCl, AlCl.sub.3, Al(OH).sub.3 and NbCl.sub.5, with a molar ratio of 24:17:10:3, were ground manually in a mortar for about 10 min until LiCl, AlCl.sub.3, Al(OH).sub.3 and NbCl.sub.5 were well mixed and no granules were observed. The mixture was transferred to a quartz tube and sealed. The mixture was then heated to 150 C. at a temperature rise rate of 5 C./min and held at this temperature for 2 h to obtain Li.sub.0.8Al.sub.0.9Nb.sub.0.1Cl.sub.2O.

Example 7

[0052] This embodiment provides a mixed-anion solid electrolyte, having a chemical formula of Li.sub.0.8Al.sub.0.9Ta.sub.0.1Cl.sub.2O, and its preparation method comprises the following steps.

[0053] In an argon-filled glove box with a water and oxygen content of less than 0.1 ppm, LiCl, AlCl.sub.3, Al(OH).sub.3 and TaCl.sub.5, with a molar ratio of 24:17:10:3, were ground manually in a mortar for about 10 min until LiCl, AlCl.sub.3, Al(OH).sub.3 and TaCl.sub.5 were well mixed and no granules were observed. The mixture was transferred to a quartz tube and sealed. The mixture was then heated to 180 C. at a temperature rise rate of 5 C./min and held at this temperature for 2 h to obtain Li.sub.0.8Al.sub.0.9Ta.sub.0.1Cl.sub.2O.

Example 8

[0054] This embodiment provides a mixed-anion solid electrolyte, having a chemical formula of Li.sub.0.7Al.sub.0.9Mo.sub.0.1Cl.sub.2O, and its preparation method comprises the following steps.

[0055] In an argon-filled glove box with a water and oxygen content of less than 0.1 ppm, LiCl, AlCl.sub.3, Al(OH).sub.3 and MoCl.sub.6, with a molar ratio of 21:17:10:3, were ground manually in a mortar for about 10 min until LiCl, AlCl.sub.3, Al(OH).sub.3 and MoCl.sub.6 were well mixed and no granules were observed. The mixture was transferred to a quartz tube and sealed. The mixture was then heated to 200 C. at a temperature rise rate of 5 C./min and held at this temperature for 2 h to obtain Li.sub.0.7Al.sub.0.9Mo.sub.0.1Cl.sub.2O.

Example 9

[0056] This embodiment provides a mixed-anion solid electrolyte, having a chemical formula of Li.sub.0.7Al.sub.0.9W.sub.0.1Cl.sub.2O, and its preparation method comprises the following steps.

[0057] In an argon-filled glove box with a water and oxygen content of less than 0.1 ppm, LiCl, AlCl.sub.3, Al(OH).sub.3 and WCl.sub.6, with a molar ratio of 21:17:10:3, were ground manually in a mortar for about 10 min until LiCl, AlCl.sub.3, Al(OH).sub.3 and WCl.sub.6 were well mixed and no granules were observed. The mixture was transferred to a quartz tube and sealed. The mixture was then heated to 200 C. at a temperature rise rate of 5 C./min and held at this temperature for 2 h to obtain Li.sub.0.7Al.sub.0.9W.sub.0.1Cl.sub.2O.

Example 10

[0058] This embodiment provides a mixed-anion solid electrolyte, having a chemical formula of Li.sub.0.8Al.sub.0.6Si.sub.0.4Cl.sub.2.2O, and its preparation method comprises the following steps.

[0059] In an argon-filled glove box with a water and oxygen content of less than 0.1 ppm, LiOH, AlCl.sub.3, Al(OH).sub.3 and SiCl.sub.4, with a molar ratio of 12:8:1:6, were ground manually in a mortar for about 10 min until LiOH, AlCl.sub.3, Al(OH).sub.3 and SiCl.sub.4 were well mixed and no granules were observed. The mixture was transferred to a quartz tube and sealed. The mixture was then heated to 200 C. at a temperature rise rate of 5 C./min and held at this temperature for 2 h to obtain Li.sub.0.8Al.sub.0.6Si.sub.0.4Cl.sub.2.2O.

Example 11

[0060] This embodiment provides a mixed-anion solid electrolyte, having a chemical formula of Li.sub.0.9Al.sub.0.9Ge.sub.0.1Cl.sub.2O, and its preparation method comprises the following steps.

[0061] In an argon-filled glove box with a water and oxygen content of less than 0.1 ppm, LiCl, AlCl.sub.3, Al(OH).sub.3 and GeCl.sub.4, with a molar ratio of 27:17:10:3, were ground manually in a mortar for about 10 min until LiCl, AlCl.sub.3, Al(OH).sub.3 and GeCl.sub.6 were well mixed and no granules were observed. The mixture was transferred to a quartz tube and sealed. The mixture was then heated to 200 C. at a temperature rise rate of 5 C./min and held at this temperature for 2 h to obtain Li.sub.0.9Al.sub.0.9Ge.sub.0.1Cl.sub.2O.

Example 12

[0062] This embodiment provides a mixed-anion solid electrolyte, having a chemical formula of Li.sub.0.8Al.sub.0.6Nb.sub.0.2Ta.sub.0.2Cl.sub.2.2O.sub.1.2, and its preparation method comprises the following steps.

[0063] In an argon-filled glove box with a water and oxygen content of less than 0.1 ppm, LiOH, AlCl.sub.3, Al(OH).sub.3, NbCl.sub.5 and TaCl.sub.5, with a molar ratio of 12:7:2:3:3, were ground manually in a mortar for about 10 min until LiOH, AlCl.sub.3, Al(OH).sub.3, NbCl.sub.5 and TaCl.sub.5 were well mixed and no granules were observed. The mixture was transferred to a quartz tube and sealed. The mixture was then heated to 200 C. at a temperature rise rate of 5 C./min and held at this temperature for 2 h to obtain Li.sub.0.8Al.sub.0.6Nb.sub.0.2Ta.sub.0.2Cl.sub.2.2O.sub.1.2.

Comparative Example 1

[0064] This embodiment provides a solid electrolyte, having a chemical formula of Li.sub.3OCl, and its preparation method comprises the following steps.

[0065] In an argon-filled glove box with a water and oxygen content of less than 0.1 ppm, LiCl and Li.sub.2O, with a molar ratio of 1:1, were ground manually in a mortar at room temperature for about 10 min until LiCl and Li.sub.2O were well mixed and no granules were observed. The mixture was transferred to a ZrO.sub.2 ball mill jar and sealed. The mixture was then ball milled in a planetary ball mill at a speed of 550 rpm for 20 h to obtain Li.sub.3OCl.

Comparative Example 2

[0066] This embodiment provides a solid electrolyte, having a chemical formula of LiAlCl.sub.4, and its preparation method comprises the following steps.

[0067] In an argon-filled glove box with a water and oxygen content of less than 0.1 ppm, LiCl and AlCl.sub.3, with a molar ratio of 1:1, were ground manually in a mortar at room temperature for about 10 min until LiCl and AlCl.sub.3 were well mixed and no granules were observed. The mixture was transferred to a ZrO.sub.2 ball mill jar and sealed. The mixture was then ball milled in a planetary ball mill at a speed of 550 rpm for 20 h to obtain LiAlCl.sub.4.

Test Example 1

1. Electrochemical Impedance Spectroscopy (EIS) and Activation Energy Testing

[0068] EIS and activation energy test were performed on the solid electrolytes of Examples 1-12 and Comparative Examples 1-2 respectively. The test methods were as follows.

[0069] 0.2 g of solid electrolyte sample powder was placed in a polytetrafluoroethylene mold with a diameter of 12 mm and pressed into a tablet. Stainless steel current collectors were mounted at two ends and sealed with sealant to isolate the electrolyte from air. The above operations were all done in the presence of argon. The Biologic electrochemical workstation was used to measure the EIS of the electrolyte at different temperatures. The conductivity and activation energy were then calculated according to the impedance of the electrolyte. The test results are shown in Table 1.

TABLE-US-00001 TABLE 1 Activation Conductivity energy Group Sample (S/cm) (eV) Example 1 Li.sub.0.8AlCl.sub.2.2O.sub.0.8 1.63 10.sup.3 0.302 Example 2 Li.sub.0.8AlCl.sub.1.8O.sub.0.8Br.sub.0.4 1.35 10.sup.3 0.330 Example 3 Li.sub.0.8AlCl.sub.1.8O.sub.0.8(BH.sub.4).sub.0.4 0.76 10.sup.3 0.380 Example 4 LiAlCl.sub.2S.sub.0.5O.sub.0.5 1.83 10.sup.3 0.295 Example 5 Li.sub.0.8AlCl.sub.1.8O.sub.0.8F.sub.0.4 0.53 10.sup.3 0.379 Example 6 Li.sub.0.8Al.sub.0.9Nb.sub.0.1Cl.sub.2O 2.53 10.sup.3 0.287 Example 7 Li.sub.0.8Al.sub.0.9Ta.sub.0.1Cl.sub.2O 2.24 10.sup.3 0.298 Example 8 Li.sub.0.7Al.sub.0.9Mo.sub.0.1Cl.sub.2O 1.93 10.sup.3 0.322 Example 9 Li.sub.0.7Al.sub.0.9W.sub.0.1Cl.sub.2O 1.74 10.sup.3 0.3241 Example 10 Li.sub.0.8Al.sub.0.6Si.sub.0.4Cl.sub.2.2O 1.95 10.sup.3 0.292 Example 11 Li.sub.0.9Al.sub.0.9Ge.sub.0.1Cl.sub.2O 1.59 10.sup.3 0.336 Example 12 Li.sub.0.8Al.sub.0.6Nb.sub.0.2Ta.sub.0.2Cl.sub.2.2O.sub.1.2 3.11 10.sup.3 0.279 Comparative Li.sub.3OCl 0.007 10.sup.3 0.643 Example 1 Comparative LiAlCl.sub.4 0.02 10.sup.3 0.580 Example 2

[0070] It can be seen from the test results in Table 1 that, compared with the electrolyte without anion or cation doping in Comparative Example 1-2, the halide electrolytes prepared in Examples 1-12 is improved by an order of magnitude in terms of conductivity and has the activation energy of Li ion migration reduced significantly, indicating that the energy of Li ions at different sites can be effectively controlled through anion and cation doping, and this is conductive to the migration of Li ions.

[0071] The schematic diagram of the conductivity of different cation-doped samples of the invention is shown in FIG. 4. It can be seen from FIG. 4 that cation doping can further improve the conductivity of the electrolyte. It indicates that on the basis of anion doping, cations replace some Al ions (Al.sup.3+), which can adjust the concentration of Li ions in the solid electrolyte and the thermodynamic stability of the electrolyte, thereby achieve the doping of more anions and further improving the ionic conductivity.

2. Structure Test of Electrolytes

[0072] Solid-state MRI and X.sup. ray diffraction (XRD) tests were performed on halide solid electrolytes of different compositions in a typical example of the invention, and the results are shown in FIGS. 2 and 3. Referring to FIG. 2, without O ion doping, there is only one kind of Li ion in LiAlCl.sub.4, and its occupied sites are octahedral voids. By doping some O ions, some Li ions can occupy other sites, such as tetrahedral voids, indicating that the doping of O ions does change the potential energy of Li ions at different sites. It can be seen from FIG. 3 that the halide solid electrolyte is in an amorphous state.

3. Electrochemical Window Test

[0073] The solid electrolyte Li.sub.0.8AlCl.sub.2.2O.sub.0.8 prepared in Example 1 and a conductive agent SP were mixed at a mass ratio of 3:7. Using 0.01 g of the resulting mixture as a cathode, a lithium tablet as an anode, and 0.14 g of the solid electrolyte Li.sub.0.8AlCl.sub.2.2O.sub.0.8 prepared in Example 1 as an electrolyte layer, a battery was assembled for cyclic voltammetry scanning (0-5V, 0.5 mV/S). The results are shown in FIG. 5.

[0074] It can be seen from the test results in FIG. 5 that the halide electrolyte Li.sub.0.8AlCl.sub.2.2O.sub.0.8 prepared in Example 1 can be used together with a commonly used cathode material to assemble a battery, and the obtained battery also has excellent cycling performance and rate performance.

4. Assembly and Testing of a Battery

[0075] Li.sub.0.8AlCl.sub.2.2O.sub.0.8 prepared in Example 1 was used as a lithium-ion halide solid electrolyte to assemble a battery. The specific steps are as follows.

[0076] Preparation of a cathode: cathode active materials LiCoO.sub.2, Li.sub.0.8AlCl.sub.2.2O.sub.0.8 (LACO) and the conductive agent SP were mixed at a mass ratio of 7:3:0.5, and the mixture was transferred to a stainless steel ball mill jar and then ball milled in a planetary ball mill at a speed of 200 rpm for 30 min to obtain a cathode powder.

[0077] Preparation of an anode: a lithium tablet and an indium tablet were laminated and pressed on a tablet press at a pressure of 20 Mpa for 10 h to obtain a LiIn alloy anode.

[0078] Assembly of a battery: the mixture of LiCoO.sub.2, Li.sub.0.8AlCl.sub.2.2O.sub.0.8 (LACO) (Example 1) and the conductive agent SP serving as a cathode, the LiIn alloy serving as an anode, and LACO and Li.sub.6PS.sub.5Cl (LPSC) serving as an electrolyte were separately pressed into tablets in a polytetrafluoroethylene mold with a diameter of 12 mm and then assembled into a LACO+LCO/LACO/LPSC/LiIn all-solid-state battery, as shown in FIG. 6. The battery was tested for cycling performance at a rate of 0.5 C at room temperature. The test results are shown in FIG. 7.

[0079] It can be seen from the test results in FIG. 7 that after 100 cycles at a rate of 0.5 C, the capacity of the LACO+LCO/LACO/LPSC/LiIn all-solid-state battery remains 91% and the Coulombic efficiency remains 99% or above, indicating that the Al-based halide solid electrolyte has good high-voltage stability and can match the high-potential cathode to achieve good cycling performance and rate performance.

[0080] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the invention belongs. The terms used herein in the specification of the present disclosure are for the purpose of describing specific embodiments only but not intended to limit the present disclosure. The term or/and used herein includes any and all combinations of one or more related listed items.

[0081] The technical features of the above-described embodiments may be arbitrarily combined. For the sake of brevity of description, all possible combinations of the technical features in the above embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, all should be considered as the scope of the present description.

[0082] The above-described embodiments only show several implementation ways of the present disclosure, which are more specific and detailed, but not to be construed as limiting the scope of the present disclosure. It should be noted that those of ordinary skill in the art may further make variations and improvements without departing from the conception of the invention, and these all fall within the scope of the invention. Therefore, the scope of the invention patent shall be subject to the appended Claims.