TW200905954A - Method of manufacturing zinc-calcium compound and zinc secondary electrode and use thereof - Google Patents

Abstract

This invention is to provide a novel chemical process for preparing the active material of a zinc secondary electrode and for improving the composition of the electrode so as to address the issues of low capacity and shortened lifespan caused by zinc electrode deformation and the formation of needle zinc during the charging and discharging of the zinc secondary electrode, the root causes of which are that zinc-calcium compound has a low solubility in potassium hydroxide electrolyte solution and that active substances are not washed away easily. The zinc-calcium compound made of the chemical process of this invention can largely increase the charging and discharging cycles of the zinc secondary electrode when applied thereto. The active substance powder made by the chemical precipitation process has great reaction uniformity and can be prepared easily. This invention employs a novel chemical precipitation process for the preparation of zinc-calcium compound, and a zinc secondary electrode made by the zinc-calcium compound is highly reversible and durable.

Description

200905954 Λ ' IX, invention description: [Technical field of invention] This solution solves the problem of zinc electrode in the process of charging/discharging of zinc secondary electrode. These problems are the secondary chemical capacity of the scale. The present invention is a new chemical method for preparing zinc. The secondary electrode is activated and the electrode formulation is modified. Deformation and generation of acicular zinc and reduction in cycle life. [Prior Art] The metal fuel cell is a kind of environmentally friendly green clean energy. It has a combination of zinc anode technology in a wide alkaline battery and air electrode technology in a fuel cell. ...The main advantage of zinc/air batteries is that they have a high energy density of about 2 吆 / 吆, and the power density is about 100~120W / kg, and the zinc / air battery can be divided into one and two according to its electrode structure. Secondary battery. The technology of one-word/air battery is relatively mature, and commercial products have been launched' mainly for 3C electronic products, such as hearing aids, mobile phones, portable computers, etc.; and the development of secondary zinc/air batteries is slow; The technology is not yet mature, but 'because the raw material cost of the battery is very low and there is no pollution, the development success will be the star of the battery in the future, which can be mainly applied to electric motor vehicles, electric vehicles, energy storage equipment, UPS, Energy storage and so on. “In many previous studies, the secondary zinc anodes were placed on how to reduce or reduce the zinc anode deformation and the dendritic enthalpy. Generally, in zinc-air batteries, the main components of zinc anodes are high-purity zinc oxide and zinc (purity of 99·5% or more) plus some additives (Bi, In, Pb, etc.) and Teflon additives (Tefi〇n binder). It is coated on a nickel foamed net (Ni-f〇am) or a nickel mesh (Ni-SCreen) to prepare a porous zinc electrode, and the cathode is an air electrode. The main component is a high specific surface area carbon black (carb〇n black). Activated carbon or graphite, precious metal or transition metal oxide catalyst, iron gas additive, etc. coated on a foamed mesh (Ni-f〇am) or nickel mesh (Ni-screen) On the substrate, the electrolyte is mainly K0H aqueous solution, the concentration of K〇H is 200905954, the ratio is: 20~40%, and the general secondary battery system is controlled at 3~WeiΚ0Η, because this is the best. At the concentration, the conductivity of the electrolyte is the best, in general, K0H electrolysis in the air battery It will not be depleted, but only the zinc pole will be oxidized to oxidize $: When the secondary battery is discharged, its cathode and anode electrochemical reactions are as follows: (+) Cathodic reaction: 1/2〇2+H2〇+ 2e — 20H —,ED=〇. 4〇v (1) (-) Anodic reaction: Zn— Zn2+ + 2e_ E°=l. 25 V (2)

Zn2++20H -> Zn(OH): Zn(0H)2—ZnO+H2〇 total reaction Zn + l/2〇2 — ZnO, E°=l. 65 V (3) in many alkaline battery systems The zinc anode is selected as the negative electrode, and the main pole has many advantages as follows: 疋Zn (1). The electrode has a lower reversible equilibrium potential (-l.25Vvs.SHE in an alkaline solution). (2) . Zinc electrodes have very good electrode dynamic behavior (less polarization). (3) • The atomic weight of zinc is not high (Zn: 65 4 g/m〇1), that is, it has a high specific energy density. (4) The zinc in the zinc electrode is cheap. (5) The preparation of the zinc electrode is easy to synthesize. (6) The metal in the electrode is not toxic, so it is environmentally friendly. (7) . Zinc electrodes have excellent safety. (8) • The zinc electrode has a low corrosion rate in an alkaline solution. (9) . The content of zinc metal on the earth is very abundant. In the literature, there are many researchers (four) published methods to improve the electrical increase of zinc electrodes. 6 200905954 ΐ Add its helium ring life, research methods mainly (four) technical improvements, such as · · zinc electrode formula added ^ = electrode, formula The formulation of the electrolyte is improved; in addition, the square, the compound, the bismuth oxide, and the electric method, and the isolation and isolation: ΐ ΐ use the pulse to charge the vibration of the zinc, and the improvement of the branch is improved. Coffee _, she Γ Τί: The improvement performance of f should not be acceptable. To be active eaieium zineate powder # _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Z_3> and Ca, 'and control the reaction temperature after jumping and pH value of n. 8 hours, then ripening (coffee) for 12 hours, and then should be dried at 120 ° C to complete the hexagonal 纴曰〗 〖%" One / month 冼 treatment, .. Liu,,, ° 曰曰 125 _ size of the compound powder. =, (calc surface Zlncate) active substance powder 'to test _ and soup t 2 ^ 0 preparations into two The secondary electrode was subjected to electrochemical analysis and the discharge method was carried out by analysis. The zinc secondary electrode prepared by them contained 350 Γ six 士, ie, 220 Zn0 +98 mg Ca(10)) 2), 10 wt.% Bi powder ( Mainly to improve the conductivity of the electrode and reduce the generation of gas, reduce the self-discharge rate) and 2 wt.% PVA polymer solution. The size of the electrode is 2 mm = x 2 cm (area 4 cm 2 ), and the thickness of the zinc electrode is about 8. And their test results found that the Ni-Zn secondary electrode made of zinc secondary electrode combined with Ni/Zn twice has a cycle life of about 1〇〇, and the discharge capacity of the compound is 200~300. mAh/g or so. In addition, other researchers in the literature found that the best electrical properties of zinc secondary electrodes made by chemically prepared barium zincate are 4〇〇~2〇〇5也cycles, then: And the zinc electrode made of the lexic powder prepared by the physical method, the electrical performance of 200,905,954 is slightly worse. They compared the zinc secondary electrodes made of general commercial ZnO and active ZnO. As a result, the electrical performance of the zinc secondary electrode is very unsatisfactory. The result is only 1〇CyCles charge and discharge life' It is a flaw in the United States. Therefore, the focus of the present invention is to prepare a zinc-calcium compound powder by a liquid phase chemical precipitation method, which is applied to a secondary zinc anode to improve the electrode composition formula and the preparation method, and the cycle life of the second word/air battery is mainly limited by Severe polarization and electrode deformation of the zinc anode. The invention adopts the liquid phase chemical precipitation method to prepare the zinc-calcium compound powder, and has the advantages of (10) reaction homogeneity and ease of preparation operation compared with the machine, the grinding method and the liquid phase chemical method. The liquid phase chemical hydrazine method was used to prepare the finished compound powder, and the material was analyzed by Raman and Raman. In addition, the completed secondary electrode, the semi-electrode electrical detection analysis, the electrochemical analysis method (touch f1, model fhemie, Netheland): cyclic voltammetry, constant current charge / Ό for systematic analysis, Thereby, the reversible electrical property of the zinc secondary electrode is enhanced, the chemical composition, uniformity, preparation method, and lifting charge/she-peak of the active (4), high energy efficiency [invention] preparation method of the compound , the party it produces. The end can be made on the secondary zinc anode, and the composition of the miscellaneous composition, uniformity, and thunder supply + including the chemical of Wenshan active material to achieve the high wheel; the electrode material is optimized to achieve ί目r, bfi4 k discharge the life of the ring. 'Preparation method of the invention of the invention, 200905954, which comprises the following steps: (1) preparing a NILOH solution of 〇l~l〇ΜNa〇n, 〇. 〇ι~5 分别, respectively The above two aqueous solutions are poured into a beaker, and uniformly stirred in a homogenizer in water to obtain a solution A, and the pH value thereof is measured; (2) Preparation of 〇. 〇1~5 Μ

Ζη(Ν〇3)2 and o.oi~5 μ Ca (N〇3> aqueous solution, mixing the two solutions in a specific ratio to obtain solution B; (3) preparing 0.01~10 M<Na〇H and 〇〇15 M of nh4〇h, the two solutions are also mixed in a specific ratio to obtain a solution c; (d) the solution B and the solution C are slowly dropped into the solution a as a titration tube, and the value of the total mixture is measured; (5) centrifugally filtering the total mixed solution and repeatedly washing with water several times, and then drying in an oven to obtain the compound powder of the dance. / In order to achieve the above object, a method for preparing a zinc secondary electrode of the present invention includes the following Steps: (1) Take appropriate amount of the compound/powder compound powder prepared by chemical sedimentation method and then add appropriate amount of zinc powder (5), appropriate amount of gold powder or metal oxide inhibitor or stabilizer and a small amount of conductive material, and place in a ball mill. Grind evenly for 1 hour; (2) Add the ground mixed powder to a suitable solvent, adhesive and other non-ionic interface-active glass beakers, and place the Wei cup in an ultrasonic mixer to make it evenly dispersed. In the solution, put the solution in the box 3, the solvent makes the liquid of the job; (3) the appropriate amount of the solution is coated on the foaming net, copper mesh, titanium mesh and fine, so that the (4) towel is properly pressed = electrode sheet; and (4) Place the electrode sheet in a high-temperature oven and sinter it. If it is smelted, the metal wire is welded and coated with epoxy resin. The preparation of the electrode is done. The person who makes the inspection can make a step-by-step understanding of the hairline structure. And the detailed description of the preferred embodiments are as follows. [Embodiment] The preparation method of the zinc compound is included in the following steps: H) Moer _, Q. G1~5 M brain H ^) Two aqueous solutions are poured into a beaker, in water, homogenizer uniform 200905954 liquid A, and its enthalpy value is measured; (2) preparation 〇〇 1~ 5m

The 3H organic salt compound is, for example but not limited to, LiOH, NH4〇H, and wherein, in the step (1), the (4) is used as a sinking agent. The sinking agent is further, for example but not limited to, Κ0Η urea, an organic salt detecting compound, and the organic compound is mixed with the various alkali metal salts of the above or other alkali metal salts of succinylamine, triethylamine, tetratriethylamine salt or the like. In the step (2), the zinc in the aqueous solution is controlled between ΐ5 ι and 1:1, and the optimum formula is between 2. 5:1. In addition, the salt and mother salt of the precursor may be Zn(N〇3)2, Zn(CH3(10)2, ZnS〇4, ZnQ〇4, Μ〇3 organic zinc salts, and the calcium salt may be Ca(N〇3>;,Ca(CH3C00)2, CaS〇4, Ca〇)3,

Ca(C2〇4), CaC12, organic calcium salt, etc., wherein the organic zinc salt may be Zn(〇R)4, R=UWl 'n=1~4, etc., and the organic calcium salt may be Ca (0R)ra, R=CnH2n+1, n=1~4, m=l, 2, and so on. In the step (4), the pH of the mixture should be controlled between 9 and 14 ± 〇 2, and the optimum pH value is 11. 5 to 12.5. After nucleation for 8 hours, stirring was continued for another 12 to 72 hours to ripen it. In the step (5), the temperature in the oven is about l〇〇QC, and the drying time is about 6 to 72 hours. Hereinafter, a possible embodiment of a method for preparing a zinc-calcium compound of the present invention and a schematic form thereof will be described in detail: Example (I): A zinc/calcium compound prepared by a chemical precipitation method, with an electron microscope 200905954 1 ,

Ohtachi 2_S SEM) and EM-mapping were used to observe the surface morphology and chemical composition. Figure (4) is a surface analysis of the word/feed compound prepared by chemical precipitation method, and the chemical sink of the powder; the pH of the temple is at 14 and can be seen as a hexagonal crystal sheet. The particles are larger. Figure (5) is a graph showing the analysis of the distribution of elements such as Zn Ca and yttrium by the scorpion 卯 (10) (Ligu, m brain analys SyStem-Quantax, Germany). It can be seen from the experimental results that there are quite a lot of Ca elements and Ζη. The elements are all coming out of the temple. In addition, Figure (6) is a zinc/contact compound #SEM image prepared by chemical precipitation method, and its sub-value is controlled at 9' during chemical precipitation of the powder. It can be clearly seen in the figure of Figure (5). The acicular structure has a very south specific surface area, and its particles are much smaller than the rhyme/mother compound with a ρΗ value of 14 (about 12 μιηη); and the figure (7) is the result of the ship analysis of the //辞 compound at ρΗ=9. It can also be seen that the distribution of the two elements of Ca and Zn is also more uniform than the value of the pH of 14 / and the compound is significantly reduced. When the powder is prepared by liquid phase chemical precipitation method, the lower the pH value, the smaller the powder particles and the larger the specific surface area. (10) When the density of the compound is _, the density is 4.40 g Μ, but at pH=14, the density is 2.6. g cm3; riding zinc oxide (ZnQ, Aldrid〇 density of 5 cm, commercially available 氲 oxidation dance (Aldrich) density is 2. 2 g cm-3). In addition, the present invention also provides a method for preparing a secondary electrode, which comprises the following steps: (1) taking an appropriate amount of a zinc compound powder prepared by a chemical method and then adding an appropriate amount of zinc powder (Zn), an appropriate amount of metal conductor powder or metal. Oxide inhibitor or stabilizer and a small amount of conductive material, placed in a ball mill to grind evenly to discard the hour; (2) Add the ground mixed powder to a suitable solvent, adhesive and other non-ionic interfaces; In a beaker, place the beaker in an ultrasonic oscillator and mix it to disperse it evenly in the solution, then place the solution in the box, remove excess & agent to form a zinc paste liquid; (3) Scale Apply an appropriate amount of zinc paste solution to the nickel foaming net, copper mesh, titanium mesh and nickel mesh, press the zinc electrode sheet with a suitable pressure in a tablet press. And (4) place the zinc electrode sheet in a high temperature oven. After sintering for several minutes, the metal wire is soldered on the zinc electrode 11 200905954 » , * and the epoxy resin is applied to complete the preparation of the zinc secondary electrode. In the meat, in the step (1), the amount of the zinc/calcium compound powder is 丨~99 wt. The amount of the zinc powder (Zn) is 15 wt.%, and the amount of the metal conductor powder is 12 〇Wt. %, the content of the metal oxide inhibitor is ^000 ppm, and the rotation speed of the ball mill is between 200 and 2000 rpm, and the grinding time is about M0 hours. Wherein, the metal conductor powder may be _-Cu, Ni powder, c 〇 powder, the metal oxide inhibitor may be PbO, Bi 2 〇 3, secret, Mg 0, Ca 〇, the stabilizer may be pEG, pEGBCME, The conductive material may be CNTs, carb〇n black_Bp2〇〇〇, etc. * In the step (2), the solvent may be H2〇, methano, IPA, ethanQl, etc., the adhesive may be PTFE binders, the non-ionic type The surfactant may be Triton-X or Tween 80, and the temperature of the oven may be 1 〇 (rc. In the step (3), the pressure of the tablet press may be 2 〇 () kgfcm 2 . The temperature in the high temperature oven is about 375 < t, and the sintering time is about 30 minutes. The principle of the method for preparing a zinc secondary electrode of the present invention will be described in detail below in the second embodiment. Example (II): I Prepared zinc/calcium compound powder (zinc: calcium molar ratio = 2. 5:1, and its pH = 9) 'Additional Zn p〇wders, suitable metal or metal oxide inhibitors or Stabilizer and a small amount of Cu (ceramics) conductive material, placed in a ball mill (bald) evenly ground Rotate _ rpm for about 2 hours. Add the ground powder to the appropriate solvent, adhesive and other non-ionic surfactants in a glass beaker. Place the ray cup on the ultrasonic recording (8) (4) cap mix. Disperse evenly in the solution towel's trap in the oven immediately after the τ, remove the excess solvent to make zine paste, and then apply a proper amount of zinc paste on the nickel foaming net. Use a tablet press to pressurize the material with a pressure of 咕(10)2. Place the zinc in a high-temperature oven towel (10) 375. Squeeze the minute. 12 200905954 t-moisturize the metal (10) wire after the zinc electrode # and apply it to Wei Na ( Epoxy), f procedures are about 2 to 4 hours, that is, the preparation of the zinc secondary electrode is completed. Table (1) is the result of the charge/discharge test of zinc two = electrode (area = 4 cm2), and the average efficiency and utilization of the zinc electrode therein The rate is about 5G%, and the energy efficiency is about the same, and the number of cycles of the zinc electrode can reach 150 times.

Extreme (A

Energy efficiency discharge rate charge/discharge number average efficiency and utilization rate

The theoretical capacity of the main zinc permanent electrode is 120 mAh. Example (3): The zinc secondary electrode prepared by the liquid phase chemical precipitation method is used for constant current charge/discharge detection. analysis. The experimental results are shown in Figure (8) and Figure (9). The active compound of the zinc electrode is prepared by chemical precipitation (ph=9); the zinc secondary electrode Bu 1〇cycies constant current charge / discharge curve. From Fig. (8) and Fig. (9), the charge curve is very stable (nat), that is, the polarization is very small. The average charging voltage in the first 5 cycles is about +45V (vs. Hg/Hg). 〇), 6 ~ 1 〇 cycle The average charging working voltage is about -1.40V, which also indicates that the zinc secondary electrode has completed the activation phase. In addition, Table (3) is the zinc electrode efficiency (%) and utilization rate (%) test results, and the chemical efficiency and utilization rate of the zinc secondary electrode (pH=9) prepared by chemical precipitation method is applied. The first 10 times are used to reach the set discharge depth (8〇%). In addition to the charge/discharge test, a zinc-zinc compound powder prepared by chemical precipitation method is prepared as a micro-zinc secondary electrode (about 1 mg of zinc active material), and a charge/discharge cycle voltammetric analysis chart is shown. The micro zinc electrode prepared by chemical precipitation method is a tiny zinc electrode prepared by chemical precipitation method. After 50 cycles of Cyclic votammetry (CV), the chemical precipitation method zinc #5 compound powder can be seen from the figure. The prepared micro zinc electrode has a better symmetry of the CV curve, and its 13 200905954 Coulomb efficiency is calculated to be almost 9 % by its cv map integral. Table (2), Zinc II also y discharge test 詖Cobalt fruit:

Note: Efficiency (%) = [actual discharge amount (mAh) / actual charge amount (mAh ^ xqoo, utilization (%) = [actual discharge capacity (mAh) / theoretical capacity (mAh)] * 100; and The theoretical capacitance of the zinc secondary electrode is 115 mAh. Table (III), Cyclic Voltammetry of Tin Electrode of Zinc Secondary Electrode

Cycle Q+ (mC) Q (mC) CE (8) Ep.a (V) Kp. c (V) ΔΕ (V) "~ip. c (mA/cm2) lp. a (mA/cm2) R value 1 11.96 128.9 9.28 - -木一- - - 10 260.1 269.7 96,44 -1.169 -1.620 0.45 1.54 0.81 0.53 20 223.5 247.9 90.16 -1.184 -1.617 0.43 1.67 0. 75 0.45 30 192.2 211.2 91.00 -1.180 -1.621 0.44 167 64 0. 38 40 167.5 180.2 92.95 -1.184 -1.611 0.43 148 60 0.41 50 147.4 160.3 91.95 -1.190 -1· 605 0.42 139 57 0.41

Note: CE = Q+/Q- (Q+ discharge, Q : charge), ΔΕ = EPa - EPC, R

Ip.c/ Ιρ·ί 14 200905954 Example (4): The zinc/calcium compound prepared by chemical precipitation method was analyzed for its crystal position and peak position and intensity by X-rib and Raman spectroscopy. Figure (11) shows the results of the chemical precipitation method and the zinc/calcium compound XRD (phi lip) structure analysis prepared by the original method. It can be seen from the towel that there are many trans-/fresh compounds prepared by Yishen County. Several crystallization peak positions are shown. Figure (12) shows the Raman spectrum of the zinc/calcium compound prepared by chemical precipitation at different pH conditions. Figure (13) shows the Raman spectrum of zinc/calcium compounds when Ca(N〇3> is mixed with Zn(N〇3)2 in different molar ratios (using the Renishaw inVia micro-Ramam spectrum analyzer, The results of the analysis were analyzed using a HeNe 633 nm laser source, 50X 〇M. Figure 14 shows the zinc/calcium compound powder at ΡΪΗ2, and the peaks are at 252 14 (w), 356. 7 (s), 428. 67 (w) is the main peak of calcium (Ca), and another is in 313.13 ϋ !? 2. % (W), 437. 94 (S) shell, and the oxidized (Zn0) Peak is located. , ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The oxidized lay ratio is similar to that of hydrogen oxyhydroxide, while the zinc prepared by the chemical hydrazine method of Fig. 15 is similar to zinc oxide. Example (5): Comparing the zinc primary electrode on different metal substrates (as the filling of sixteen) is the recording foaming net as the substrate, and most of the zinc active substances are equally divided into the outermost species of nickel^ The active material f ZnGa is alive, and the copper mesh (Cu-screen) and titanium mesh (Ti *', negative micromirror (0M) surface analysis map, Tus, : 甘甘_LL / Λ1 network 'copper network domain coffee ΛΕ 织 = ==== 15 200905954 E value is based on metal titanium mesh zinc electrode is significantly lower than the other two, ^ ^ value is small, that is, small polarization, charge and discharge The reversibility is good, and the figure (20) is the change of the coulombic efficiency and the zinc utilization rate of the three substrates on the experimental results of the charge and discharge times. The experimental results show that the metal titanium mesh is the secondary electrode of the current collector substrate. The efficiency of the library stealing is higher. The figure (21) is energy, and the efficiency (%) shows the change of the charge/discharge times. The experimental results also show that the energy efficiency of the metal titanium mesh is better than that of the copper mesh tin and the nickel mesh tin. It is high. Example (6): In addition to the preparation of zinc/secondary electrode by chemical deposition method, it will also be added. Calcium ion in the 4M Κ0Η electrolyte solution formulation, Figure (22) and Figure (23) for the comparison of the addition of calcium ions in the electrolyte solution formulation before the impact of the figure (24) and the map (twenty-five hemp Adding _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Example (7): The best zinc II: when it is miscellaneously branched, it is a kind of composite polymer structure. Under the (10)_ liquid formula, its ΔΕ value is analyzed for the number of cycles. ^ Efficiency is 49. 75%, efficiency and zinc utilization rate are shown in the cycle number ^ ' = one =. In addition, the current quantity efficiency is shown in the cycle number, as shown in ®^27); The disclosed person is shown as 1 =® (-18). One of the best examples, the partial change or the repair of the technical ideas of the case is based on the technical idea of the case. ^ The person who learns the skill is easy to infer, and in the case, the means and the effect of the case,侔μf firstly became practical and practical, and also in the society in line with the invention, the real sense of Deyi / a member of the inspection, and analysis of the early patent, Zhai Jiahui [simple description of the schema] prepared 4 for the tender deletion of hydration riding hydrogen peroxide Figure 1 shows the schematic diagram of the secondary electrode with the composite pvA polymer separator. Figure 4 shows the zinc/calcium compound value prepared by chemical precipitation method. Figure 5 is an EDX mapping analysis of the zinc/dancing compound (Qiu 14) prepared by chemical precipitation. Figure 6 is a SEM analysis of the zinc/calcium compound (pH 9) prepared by chemical precipitation. The EDX mapping analysis of the word/calcium compound (pH 9) prepared by chemical precipitation method. Figure 8 is a graph of the charge/discharge curve of the zinc chemical secondary precipitation l-5 cycle. Figure 9 is a graph of the charge/discharge curve of a zinc chemical 6-10 cycle. Figure 10 is a speech - - chemical precipitation After 50 cycles of charge / discharge cycle voltammogram. Figure 11 is a comparative analysis of the zinc/dancing compound beach structure prepared by the chemical precipitation method and the current method. =12 is a Raman spectrum of a zinc/calcium compound prepared by chemical hydration at a unique pH. = thirteen is different (^(10)仏 and (10)〇2 mixed ratio 砰, Raman spectrum of zinc/calcium compound. ^ Four is the Raman spectral oxidation of zinc/about compound at pH 12 (City map cross) -section) Sixteen is the SEM cross section of the zinc secondary electrode (Figure 17 is the SEM image of the tin plating of the copper mesh. Figure 18 is the optical microscope image of the titanium mesh (〇M). Value: t is the discharge-electricity 4 Change (= analysis: net - * 丄 二 和录网) can be =: in the electrolytic formula formula Zhongjing solution formula in the medium formula solution in the solution 18 200905954 I ί Figure 26 is the zinc secondary electrode Figure 27 shows the analysis of the current efficiency and zinc utilization of the zinc secondary electrode on the cycle number. Figure 28 shows the analysis of the energy efficiency of the zinc secondary electrode versus the cycle number. [Main component symbol description] None 0 19

Claims (1)

200905954 X. Patent application scope: (- It includes the following steps: uniform rapid stirring to obtain a solution, in water 'to homogenize machine (one W system η Γ and A and measure its PH value; two melt ping, >r *HB and solution^ slowly drip into solution A: the pH value of the total mixture; and the batch Φ5 i, the total mixture is centrifuged and washed several times, then placed in /, phase dried That is, the _ compound powder is obtained. The preparation method of the hetero compound described in the method of the formula 1 is used as a sputum agent. The _ system is used as a precipitating agent, and the preparation of the compound of the second item of the π application patent range is described. The organic salt test agent may further be K〇H, L i〇H, NH4〇H, urea, U, and the preparation range of the compound of the above-mentioned 4th. The organic salt test compound may be diethylamine. a triethylamine, a monoamine salt, or the like, or a mixture of various alkali metal salts, etc. The method of preparing the ankle compound described in the patent formula 1 is in the axial solution of γ ΓΓΙϊ and if solution. The ratio is controlled to between 1.1 and the optimal formula is between 2: 5: 1. 6. If the patent application scope is 帛 1 item 5~12。 The pH value of the mixture is between 9 and 14 ± 0.2, and the optimum pH value is 11. 5~12 · 5, after that, in the air isolation state, stirring for 8 hours to make it nucleate stable, and then continue to stir for 12 to 72 hours to make it mature. 7. Preparation of zinc calcium compound according to claim 1 The method of the present invention, wherein the temperature in the oven is about 1 Torr, and the drying time is about 6 to 72 hours. 8. The preparation method of the calcium compound according to the first aspect of the patent application, wherein In the step (2), the salt and calcium salt of the precursor may be "Zn(N〇3)2, Zn(CH3COO)2, ZnS〇4, ZnC2〇4, ZnC〇3, ZnS〇4, ZnCl2, organic salt, calcium salt may be Ca(N〇3)2, Ca(CH3C〇〇)2, CaS〇4, CaC〇3, Ca(C2〇4), CaCl2, organic #5 salt, etc. 9. The method for preparing a zinc-calcium compound according to claim 8, wherein the organic zinc salt may be Zn(0R)4, R=CnH2n+1, η=Bu4, etc., the organic calcium Salt Ca(0R)m, R=CnH2n+1, η = 1~4 m=l, 2, etc. ' 10. A method for preparing a zinc secondary electrode, comprising the following steps: (1) taking an appropriate amount Zinc/calcium compound powder prepared by chemical precipitation method ^ Add appropriate amount of zinc powder (Zn), appropriate amount of metal conductor powder or metal oxide inhibitor or stabilizer and a small amount of conductive material, and place in a ball mill to evenly stir 1~10 (2) Add the ground mixed powder to a suitable solvent, adhesive and other non-ionic surfactant in a glass beaker, and place the beaker in an ultrasonic oscillator and mix and mix it evenly in the solution. Then place the solution in an oven to remove excess solvent to form a zinc paste-like liquid. (3) Apply an appropriate amount of zinc paste solution to the nickel foaming net, copper, mesh, titanium mesh and nickel mesh. The tablet press is pressed at a suitable pressure into a zinc electric 21 200905954 pole piece; and a preparation process of the zinc secondary electrode. F疋成u·Zinc secondary electrode shear as described in claim 10 of the patent scope: public: step: Guangzhong - amount of compound powder ^ knife (n) amount is 1~15 wt. %, metal conductor The amount of powder east is 20 wt.%, the content of metal oxide is 5%, and the rotation speed of the ball mill is about 10 hours. Between rpm, the grinding time is ready! The zinc secondary electrode system described in the eleventh patent is c〇ί too: the conductor powder can be coffee_cu, Ni powder, and the final U metal oxide inhibitor can be pb0 , Bi203, In, / m The stabilizer can be PEG, PEGBCME, the conductive material can be '', s, carbon black-BP2000, and the like. In the TPA of the zinc secondary electrode described in Item 10 of the patent scope, in the step (2), the solvent may be H2〇, methan〇l, subtype boundary e = temperature may be loot or Tween 80 'The oven of the oven, such as the application of the patent scope of the tenth item of the second electrode of the production of kgfem2', in this step (three), the pressure of the tablet press can be 200 Γ, ϊΓΐϊΞ range In the O7rop ^ T涿 step (4) of the zinc secondary electrode according to item 10, the temperature in the high temperature oven is about 30 minutes. The method for preparing a zinc-electrode 22 200905954-one human electrode according to any one of claims 5 to 5, wherein the prepared zinc secondary electrode can be used in combination with a solid solid PVA polymer separator for charging/discharging. The composite solid PVA polymer separator has high ionic conductivity (1(Γΐ~1〇—35επΓΐ) and porosity, and the high ionic conductivity property can reduce the resistance of the electrode and the ohmic drop polarization degree. Etc., and the porous property can effectively discharge the gas to reduce swelling and increase the coulombic efficiency. The composite solid pvA polymer separator contains ceramic ceramics (ceramic fin=s) powder, and the surface area and size of the powder are increased. The absorption of the electrolyte improves the mechanical and thermal properties, wherein the nano ceramic filled powder can be TK) 2, Zr〇2, Si〇2' BaTi〇2, Mgo, Ce〇2, Fe2〇3, γ2〇 The method for preparing a zinc secondary electricity f according to any one of claims 1 to 15, wherein the zinc secondary electrode further comprises a solid-state PVA polymer film electrolysis 'Charging/discharging Y need to first test zinc secondary counter electrode immersed in the coffee for about 12~72 hours H2M of the electrolyte. The method for preparing a secondary electrode according to any one of claims 10 to 15, wherein the prepared zinc secondary electrode is charged with a theoretical charge capacity of 10 to 5 % of charge, and When discharging, the electromagnetism can be electrically reversed at a theoretical capacity of 50 to 95%, and avoid the secondary electricity. The preparation method according to any one of claims 1 to 15 of the patent application The secondary electrode can be prepared into various large "the same shape, different size area, different capacitance of the electrode into a mine; ^ it zinc electrode use, it can be used with a variety of different positive = same use ' can be applied once and Secondary battery or fuel 23 200905954 21. The use of a zinc electrode according to claim 20, wherein the positive electrode can be an air electrode, nickel hydroxide (positive electrode), Ag or MnO, or the like.