Treatment method for preparing zirconium oxide solid electrolyte tube

Abstract

The invention relates to the technical field of preparation of zirconium oxide solid electrolyte tubes, in particular to a treatment method for preparing a zirconium oxide solid electrolyte tube. The method comprises the following steps: respectively obtaining n1 temperature values, n2 magnesium oxide mass values and n3 barium carbonate mass values from a specified temperature range, a specified magnesium oxide mass range and a specified barium carbonate mass range at equal intervals; obtaining an optimal adding speed Vijk when the sodium oxide crystal is heated to Ti and magnesium oxide with the mass of Mj and barium carbonate with the mass of Bk are added into the sodium chloride solution; obtaining target weights w1, w2 and w3 of the temperature, the magnesium oxide mass and the barium carbonate mass according to the Vijk; obtaining a target relationship according to the w1, the w2 and the w3; and according to the target relationship, obtaining the optimal adding speed of heating the sodium oxide crystal to T 'and adding magnesium oxide with the mass of M' and barium carbonate with the mass of B 'into the sodium chloride melt. According to the method, the performance of the prepared zirconium oxide solid electrolyte tube can be improved.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of zirconium oxide solid electrolyte tubes, and in particular to a processing method for preparing zirconium oxide solid electrolyte tubes. Background Art

[0002] A Chinese patent application with publication number CN113430330A discloses a method for preparing a zirconium oxide solid electrolyte tube and an oxygen measurement probe. The method for preparing a zirconium oxide solid electrolyte tube disclosed in the patent application comprises: heating a first mass of sodium chloride crystals to a molten state; adding a second mass of magnesium oxide and a third mass of barium carbonate to the molten sodium chloride, mixing, and obtaining a solid mixture after cooling; and processing the solid mixture into a zirconium oxide tube for an oxygen measurement probe.

[0003] Although the above patent application discloses a method for preparing a zirconium oxide solid electrolyte tube, the method does not involve the relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide and the mass of barium carbonate, and the optimal speed of adding magnesium oxide and barium carbonate. However, the speed of adding magnesium oxide and barium carbonate directly affects the conductivity and stability of the finally prepared zirconium oxide solid electrolyte tube. How to obtain the optimal speed of adding magnesium oxide and barium carbonate is an urgent problem to be solved. Summary of the invention

[0004] The object of the present invention is to provide a processing method for preparing a zirconium oxide solid electrolyte tube, so as to obtain an optimal speed for adding magnesium oxide and barium carbonate, and to improve the conductivity and stability of the prepared zirconium oxide solid electrolyte tube.

[0005] According to the present invention, a processing method for preparing a zirconium oxide solid electrolyte tube is provided, the method comprising the following steps:

[0006] S100, obtaining n1 temperature values ​​at equal intervals from a specified temperature range, obtaining n2 magnesium oxide mass values ​​at equal intervals from a specified magnesium oxide mass range, and obtaining n3 barium carbonate mass values ​​at equal intervals from a specified barium carbonate mass range; n1, n2 and n3 are respectively the first preset value number, the second preset value number and the third preset value number.

[0007] S200, obtain the sodium oxide crystals heated to T i , the mass is M j The magnesium oxide and mass B k The optimal addition rate V when adding barium carbonate to sodium chloride solution ijk ; T i is the i-th temperature value obtained from the specified temperature range at equal intervals, and the value range of i is 1 to n1; M jis the jth magnesium oxide mass value obtained from the specified magnesium oxide mass range with equal spacing, and the value range of j is 1 to n2; B k is the kth barium carbonate mass value obtained from the specified barium carbonate mass range at equal intervals, where k ranges from 1 to n3.

[0008] S300, according to V ijk The target weight w1 of the temperature, the target weight w2 of the mass of the magnesium oxide, and the target weight w3 of the mass of the barium carbonate are obtained.

[0009] S400, obtaining a target relationship between the temperature to which the sodium oxide crystals are heated, the mass of the added magnesium oxide, the mass of the added barium carbonate, and the optimal adding speed based on w1, w2, and w3.

[0010] S500, obtaining an optimal adding speed for heating the sodium oxide crystals to T' and adding magnesium oxide with a mass M' and barium carbonate with a mass B' into the sodium chloride melt according to the target relationship, the target temperature value T', the target magnesium oxide mass M' and the target barium carbonate mass B'.

[0011] Compared with the prior art, the present invention has at least the following beneficial effects:

[0012] The present invention obtains multiple values ​​at equal intervals from a specified temperature range, magnesium oxide mass range and barium carbonate mass range, can fully cover the parameter range, and can obtain the optimal addition speed under different temperature, magnesium oxide mass and barium carbonate mass combinations, so as to more comprehensively understand the influence of these factors on the optimal addition speed; the present invention simultaneously considers the influence of the three key factors of temperature, magnesium oxide mass and barium carbonate mass on the optimal addition speed, and obtains the weights of temperature, magnesium oxide mass and barium carbonate mass based on the optimal addition speed under the above-mentioned different temperature, magnesium oxide mass and barium carbonate mass combinations, and establishes the relationship between temperature, magnesium oxide mass and barium carbonate mass and the optimal addition speed. Based on the relationship, it can provide operational guidance for the optimal addition speed for preparing zirconium oxide solid electrolyte tubes, which is beneficial to improving the conductivity, stability and other properties of the prepared zirconium oxide solid electrolyte tubes. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0014] Figure 1 A flow chart of a processing method for preparing a zirconium oxide solid electrolyte tube provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0015] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0016] According to this embodiment, Figure 1 As shown, a processing method for preparing a zirconium oxide solid electrolyte tube is provided, and the method comprises the following steps:

[0017] S100, obtaining n1 temperature values ​​at equal intervals from a specified temperature range, obtaining n2 magnesium oxide mass values ​​at equal intervals from a specified magnesium oxide mass range, and obtaining n3 barium carbonate mass values ​​at equal intervals from a specified barium carbonate mass range; n1, n2 and n3 are respectively the first preset value number, the second preset value number and the third preset value number.

[0018] In this embodiment, n1=n2=n3 or n1≠n2≠n3. Optionally, n1, n2 and n3 are all empirical values.

[0019] As a specific implementation, the specified temperature range is 800-900°C, the specified magnesium oxide mass range is 6.4-9.2 grams, the specified barium carbonate mass range is 25-50 grams; the particle size range of magnesium oxide is 50-150 nanometers, the purity of barium carbonate is greater than or equal to 99.5%, and the sodium chloride melt is obtained from 1000 grams of sodium oxide crystals.

[0020] S200, obtain the sodium oxide crystals heated to T i , the mass is M j The magnesium oxide and mass B k The optimal addition rate V when adding barium carbonate to sodium chloride solution ijk ; T i is the i-th temperature value obtained from the specified temperature range at equal intervals, and the value range of i is 1 to n1; M j is the jth magnesium oxide mass value obtained from the specified magnesium oxide mass range with equal spacing, and the value range of j is 1 to n2; B k is the kth barium carbonate mass value obtained from the specified barium carbonate mass range at equal intervals, where k ranges from 1 to n3.

[0021] It should be understood that heating the sodium oxide crystals to T i , the mass is M j The magnesium oxide and mass B k When barium carbonate is added to the sodium chloride solution, V ijkAs the rate of adding magnesium oxide and barium carbonate can obtain a zirconium oxide solid electrolyte tube with better performance. Optionally, V ijk Obtained through experimentation, or as experience points.

[0022] S300, according to V ijk The target weight w1 of the temperature, the target weight w2 of the mass of the magnesium oxide, and the target weight w3 of the mass of the barium carbonate are obtained.

[0023] In this embodiment, if the mass of magnesium oxide added is the same and the mass of barium carbonate added is the same, but the optimal addition speeds corresponding to different temperatures are quite different, then the target weight of temperature is greater; as a preferred specific implementation, S300 includes:

[0024] S310, obtain the mass M j The magnesium oxide and mass B k The optimal addition rate set V when adding barium carbonate to sodium chloride solution jk ; V jk = {V 1jk ,V 2jk ,…,V ijk ,…,V n1jk}.

[0025] S320, according to V jk The entropy gain will be M j The magnesium oxide and mass B k The initial weight Tw of the temperature when barium carbonate is added to the sodium chloride melt jk .

[0026] As a specific implementation, Tw jk =(1-E jk ) / (∑ n2 j＝1 ∑ n3 k＝1 (1-E jk )), E jk For V jk The entropy of a set is normalized. It is known to those skilled in the art that any method for obtaining the entropy of a set in the prior art falls within the protection scope of the present invention.

[0027] S330, {Tw1, Tw2, …, Tw k ,…,Tw n3 The average initial weight of} is determined as the first specified weight Tw of temperature; Tw k is the kth subset of the initial temperature weight set, Tw k ={Tw 1,k ,Tw 2,k ,…,Twj,k ,…,Tw n2,k}.

[0028] In this embodiment, the larger w1 is, the greater the influence of temperature on the optimal adding speed is.

[0029] S340, determining Tw / (Tw+Mw+Bw) as w1; Mw and Bw are the first designated weight of the mass of magnesium oxide and the first designated weight of barium carbonate, respectively.

[0030] Based on S310-S340, the influence of temperature factors on the optimal addition rate can be measured according to the entropy of the optimal addition rate corresponding to different temperatures for the same mass of magnesium oxide and the same mass of barium carbonate, and the weight of temperature for the optimal addition rate when the temperature is within the specified temperature range can be obtained more accurately.

[0031] Based on a similar method, w2 and w3 can be obtained, wherein obtaining w2 includes: obtaining heating the sodium oxide crystal to T i and the mass is B k The optimal addition rate set when adding barium carbonate to the sodium chloride melt; according to the entropy of the set, the sodium oxide crystal is heated to T i and the mass is B k The initial weight Mw of magnesium oxide when barium carbonate is added to sodium chloride solution ik ; {Mw1,Mw2,…,Mw k ,…,Mw n3 The average initial weight of} is determined as the first specified weight Mw of the mass of magnesium oxide; Mw k is the kth subset of the initial weight set of magnesium oxide mass, Mw k = {Mw 1,k ,Mw 2,k ,…,Mw i,k ,…,Mw n1,k}; Mw / (Tw+Mw+Bw) is determined as w2. Wherein, obtaining w3 includes: obtaining heating the sodium oxide crystal to T i and the mass is M j The optimal addition rate set when magnesium oxide is added to the sodium chloride melt; the sodium oxide crystal is heated to T according to the entropy of the set. i and the mass is M j The ijth initial weight Bw of the mass of barium carbonate when magnesium oxide is added to the sodium chloride melt ij ; {Bw1,Bw2,…,Bw i ,…,Bw n1 The average initial weight of} is determined as the first specified weight Bw of the barium carbonate mass; Bw i is the i-th subset of the initial weight set of barium carbonate mass, Bwi = {Bw i,1 ,Bw i,2 ,…,Bw i,j ,…,Bw i,n2}; Determine Bw / (Tw+Mw+Bw) as w3.

[0032] S400, obtaining a target relationship between the temperature to which the sodium oxide crystals are heated, the mass of the added magnesium oxide, the mass of the added barium carbonate, and the optimal adding speed based on w1, w2, and w3.

[0033] In this embodiment, the target relationship is used to characterize the relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate, wherein the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, and the mass of barium carbonate added are independent variables, and the optimal addition rate is a dependent variable. As a preferred specific implementation, S400 includes:

[0034] S410, obtaining a first initial relationship of v=w1×t+w2×m+w3×b; wherein t, m and b are respectively the normalized temperature, mass of magnesium oxide and mass of barium carbonate, and v is a coefficient of an optimal adding speed obtained according to the normalized temperature, mass of magnesium oxide and mass of barium carbonate.

[0035] In this embodiment, the corresponding relationship between the coefficient of the optimal addition speed and the true value of the optimal addition speed can be known, for example, it can be obtained through experiments; based on the corresponding relationship and the coefficient of the optimal addition speed, the true value of the optimal addition speed can be known.

[0036] Those skilled in the art are aware that any normalization processing method in the prior art falls within the protection scope of the present invention.

[0037] S420, obtaining the accuracy of the first initial relationship according to a test sample set; the test sample set includes a plurality of test samples, and any test sample includes a temperature value, a mass value of magnesium oxide, a mass value of barium carbonate, and an optimal addition speed value.

[0038] In this embodiment, if the temperature value, the mass of magnesium oxide and the mass of barium carbonate included in a test sample are respectively normalized and inserted into the first initial relationship, the coefficient of the optimal addition speed can be obtained, and the true value of the optimal addition speed can be obtained according to the coefficient of the optimal addition speed. If the difference between the true value and the optimal addition speed value included in the test sample is less than or equal to a preset speed difference threshold, the test sample is determined to be a positive sample of the first initial relationship; the ratio of the number of positive samples of the first initial relationship included in the test sample set to the number of test samples included in the test sample set is determined as the accuracy of the first initial relationship. Optionally, the speed difference threshold is an empirical value.

[0039] S430: If the accuracy of the first initial relationship is greater than or equal to a preset accuracy threshold, determine the first initial relationship as a target relationship.

[0040] In this embodiment, the preset accuracy threshold is an empirical value.

[0041] Based on S410-S430, the target relationship can be accurately obtained when w1, w2 and w3 can accurately characterize the relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added and the mass of barium carbonate added and the optimal addition rate.

[0042] As a preferred specific implementation, S430 further includes: if the accuracy of the first initial relationship is less than a preset accuracy threshold, entering S440.

[0043] S440, obtaining n1 temperature values ​​at equal intervals from a first sub-temperature range, and obtaining n1 temperature values ​​at equal intervals from a second sub-temperature range; the first sub-temperature range is the first half of the specified temperature range, and the second sub-temperature range is the second half of the specified temperature range.

[0044] In this embodiment, if the specified temperature range is 800-900°C, the first sub-temperature range is 800-850°C, and the second sub-temperature range is 850-900°C.

[0045] S450, obtain the sodium oxide crystals heated to C - i , the mass is M j The magnesium oxide and mass B k The optimal addition rate VC when adding barium carbonate to sodium chloride solution - ijk , and obtain the sodium oxide crystals heated to C + i , the mass is M j The magnesium oxide and mass B kThe optimal addition rate VC when adding barium carbonate to sodium chloride solution + ijk ; C - i is the ith temperature value obtained from the first sub-temperature range with equal spacing, C + i is the i-th temperature value obtained from the second sub-temperature range at equal intervals.

[0046] Optional, VC - ijk and VC + ijk Obtained through experimentation, or as experience points.

[0047] S460, according to VC - ijk Get the target weight w of the temperature in the first sub-temperature range - 1, and according to VC + ijk Get the target weight w of the temperature in the second sub-temperature range + 1.

[0048] In this embodiment, according to VC - ijk Get the target weight w of the temperature in the first sub-temperature range - 1 process and according to VC + ijk Get the target weight w of the temperature in the second sub-temperature range + 1 process are based on V ijk The process of obtaining the target weight w1 of the temperature is similar and will not be repeated here.

[0049] S470, if w - 1 and w + 1 is greater than the preset difference value threshold, then according to w - 1. w2 and w3 obtain the first sub-initial relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate, and according to w + 1. w2 and w3 obtain the second sub-initial relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate.

[0050] In this embodiment, if w - 1 and w + 1 is greater than the preset difference value threshold, indicating that the temperature in the first sub-temperature range and the second sub-temperature range has different effects on the optimal adding speed. In this case, this embodiment respectively adjusts the optimal adding speed according to w -1. w2 and w3 obtain the first sub-initial relationship and according to w + 1. w2 and w3 obtain the second sub-initial relationship; it should be understood that the first sub-initial relationship characterizes the relationship between the temperature in the first sub-temperature range, the mass of magnesium oxide and the mass of barium carbonate and the optimal addition rate, and the second sub-initial relationship characterizes the relationship between the temperature in the second sub-temperature range, the mass of magnesium oxide and the mass of barium carbonate and the optimal addition rate.

[0051] S480: If the accuracy rates of the first sub-initial relationship and the second sub-initial relationship are both greater than or equal to a preset accuracy threshold, the first sub-initial relationship and the second sub-initial relationship are determined as target relationships.

[0052] In this embodiment, the process of determining the accuracy of the first sub-initial relationship and the process of determining the accuracy of the second sub-initial relationship are similar to the process of determining the accuracy of the first initial relationship, and will not be repeated here.

[0053] Based on S440-S480, - 1, w2 and w3 can accurately characterize the relationship between the heating of the sodium oxide crystals to a temperature within the first sub-temperature range, the mass of magnesium oxide added, the mass of barium carbonate added and the optimal addition rate, and w + 1. When w2 and w3 can accurately characterize the relationship between heating the sodium oxide crystals to a temperature within the second sub-temperature range, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate, the target relationship can be accurately obtained.

[0054] As a preferred specific implementation, S480 further includes: if the accuracy of the first sub-initial relationship is greater than or equal to a preset accuracy threshold and the accuracy of the second sub-initial relationship is less than the preset accuracy threshold, then entering S481.

[0055] S481, obtaining n1 temperature values ​​at equal intervals from the first sub-temperature range, and obtaining n1 temperature values ​​at equal intervals from the second sub-temperature range; the first sub-temperature range is the first half temperature range of the second sub-temperature range, and the second sub-temperature range is the second half temperature range of the second sub-temperature range.

[0056] In this embodiment, if the second sub-temperature range is 850-900°C, then the first sub-temperature range is 850-875°C, and the second sub-temperature range is 875-900°C.

[0057] S482, obtain the sodium oxide crystals heated to C 2- i , the mass is M j The magnesium oxide and mass B kThe optimal addition rate VC when adding barium carbonate to sodium chloride solution 2- ijk , and obtain the sodium oxide crystals heated to C 2+ i , the mass is M j The magnesium oxide and mass B k The optimal addition rate VC when adding barium carbonate to sodium chloride solution 2+ ijk ; C 2- i is the ith temperature value obtained from the first temperature range with equal spacing, C 2+ i is the i-th temperature value obtained at equal intervals from the second sub-temperature range.

[0058] Optional, VC 2- ijk and VC 2+ ijk Obtained through experimentation, or as experience points.

[0059] S483, according to VC 2- ijk Get the target weight w of the temperature in the first temperature range 2- 1, and according to VC 2+ ijk Get the target weight w of the temperature in the second temperature range 2+ 1.

[0060] In this embodiment, according to VC 2- ijk Get the target weight w of the temperature in the first temperature range 2- 1 process and according to VC 2+ ijk Get the target weight w of the temperature in the second temperature range 2+ 1 process are based on V ijk The process of obtaining the target weight w1 of the temperature is similar and will not be repeated here.

[0061] S484, if w 2- 1 and w 2+ 1 is greater than the preset difference value threshold, then according to w 2- 1. w2 and w3 obtain the first initial relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate, and ... 2+ 1. w2 and w3 obtain the second initial relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate.

[0062] In this embodiment, if w 2- 1 and w 2+ 1 is greater than the preset difference value threshold, indicating that the temperature has different effects on the optimal addition speed when it is in the first sub-temperature range and the second sub-temperature range. In this case, this embodiment uses w 2- 1. w2 and w3 obtain the first initial relationship and according to w 2+ 1. w2 and w3 obtain the second sub-initial relationship; it should be understood that the first sub-initial relationship characterizes the relationship between the temperature in the first sub-temperature range, the mass of magnesium oxide and the mass of barium carbonate and the optimal addition rate, and the second sub-initial relationship characterizes the relationship between the temperature in the second sub-temperature range, the mass of magnesium oxide and the mass of barium carbonate and the optimal addition rate.

[0063] S485: If the accuracy of the first sub-initial relationship and the second sub-initial relationship are both greater than or equal to a preset accuracy threshold, the first sub-initial relationship, the first sub-initial relationship and the second sub-initial relationship are determined as target relationships.

[0064] In this embodiment, the process of determining the accuracy of the first initial relationship and the process of determining the accuracy of the second initial relationship are similar to the process of determining the accuracy of the first initial relationship, and will not be repeated here.

[0065] Based on S481-S485, in w - 1. When w2 and w3 can accurately characterize the relationship between heating the sodium oxide crystals to a temperature within the first sub-temperature range, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate, w 2- 1. w2 and w3 can accurately characterize the relationship between the heating of the sodium oxide crystals to a temperature within the first temperature range, the mass of magnesium oxide added, the mass of barium carbonate added and the optimal addition rate, and w 2+ 1. When w2 and w3 can accurately characterize the relationship between heating the sodium oxide crystals to a temperature within the second temperature range, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate, the target relationship can be accurately obtained.

[0066] In this embodiment, if the accuracy of the initial relationship is less than the accuracy threshold, the temperature interval corresponding to the initial relationship is divided; preferably, the binary method is used to continuously divide the temperature interval corresponding to the initial relationship whose accuracy is less than the accuracy threshold, until the difference between the target weights of the temperatures of the two temperature intervals obtained after the last division is less than or equal to the preset difference value threshold.

[0067] As a preferred specific implementation, S470 further includes: if w -1 and w + If the difference value of 1 is less than or equal to the preset difference value threshold, the process proceeds to S471.

[0068] In this embodiment, if w - 1 and w + A difference value of 1 is less than or equal to the preset difference value threshold, indicating that the effect of the temperature on the optimal addition speed when the temperature is in the first sub-temperature range is relatively consistent with the effect of the temperature on the optimal addition speed when the temperature is in the second sub-temperature range.

[0069] S471, obtaining n2 magnesium oxide mass values ​​at equal intervals from a first sub-magnesium oxide mass range, and obtaining n2 magnesium oxide mass values ​​at equal intervals from a second sub-magnesium oxide mass range; the first sub-magnesium oxide mass range is the first half of the specified magnesium oxide mass range, and the second sub-magnesium oxide mass range is the second half of the specified magnesium oxide mass range.

[0070] In this embodiment, if the mass range of the specified magnesium oxide is 6.4-9.2 grams, the mass range of the first sub-magnesium oxide is 6.4-7.8 grams, and the mass range of the second sub-magnesium oxide is 7.8-9.2 grams.

[0071] S472, obtain the sodium oxide crystals heated to T i , the mass is P - j The magnesium oxide and mass B k The optimal addition rate VP when adding barium carbonate to sodium chloride solution - ijk , and obtain the sodium oxide crystals heated to T i , the mass is P + j The magnesium oxide and mass B k The optimal addition rate VP when adding barium carbonate to sodium chloride solution + ijk ;P - j is the jth MgO mass value obtained from the first sub-MgO mass range with equal spacing, P + j is the jth magnesium oxide mass value obtained from the second sub-magnesium oxide mass range with equal spacing.

[0072] Optional, VP - ijk and VP + ijk Obtained through experimentation, or as experience points.

[0073] S473, according to VP - ijkGet the target weight w of the magnesium oxide mass in the first sub-magnesium oxide mass range - 2, and according to VP + ijk Get the target weight w of the magnesium oxide mass in the second sub-magnesium oxide mass range + 2.

[0074] In this embodiment, according to VP - ijk Get the target weight w of the magnesium oxide mass in the first sub-magnesium oxide mass range - 2 process and according to VP + ijk Get the target weight w of the magnesium oxide mass in the second sub-magnesium oxide mass range + 2 processes are based on V ijk The process of obtaining the target weight w2 of the mass of magnesium oxide is similar and will not be repeated here.

[0075] S474, if w - 2 and w + 2 is greater than the preset difference value threshold, then according to w1, w - 2 and w3 obtain the third sub-initial relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate, and according to w1, w + 2 and w3 obtain the fourth sub-initial relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate.

[0076] In this embodiment, if w - 2 and w + 2 is greater than the preset difference value threshold, indicating that the influence of the magnesium oxide mass in the first sub-magnesium oxide mass range and the second sub-magnesium oxide mass range on the optimal addition rate is different. In this case, this embodiment uses w1, w2, and w3 as the input parameters, respectively. - 2 and w3 obtain the third sub-initial relationship and according to w1, w + 2 and w3 obtain the fourth sub-initial relationship; it should be understood that the third sub-initial relationship characterizes the relationship between temperature, the mass of magnesium oxide and the mass of barium carbonate in the first sub-magnesium oxide mass range and the optimal addition rate, and the fourth sub-initial relationship characterizes the relationship between temperature, the mass of magnesium oxide and the mass of barium carbonate in the second sub-magnesium oxide mass range and the optimal addition rate.

[0077] S475: If the accuracy rates of the third sub-initial relationship and the fourth sub-initial relationship are both greater than or equal to a preset accuracy threshold, the third sub-initial relationship and the fourth sub-initial relationship are determined as target relationships.

[0078] In this embodiment, the process of determining the accuracy of the third sub-initial relationship and the process of determining the accuracy of the fourth sub-initial relationship are similar to the process of determining the accuracy of the first initial relationship, and will not be repeated here.

[0079] Based on S471-S475, in w1, w - 2 and w3 can accurately characterize the relationship between the temperature at which the mass of magnesium oxide is within the first sub-magnesium oxide mass range, the mass of magnesium oxide added, the mass of barium carbonate added and the optimal addition rate, and w1, w + When w2 and w3 can accurately characterize the relationship between the temperature at which the mass of magnesium oxide is within the second sub-magnesium oxide mass range, the mass of magnesium oxide added, the mass of barium carbonate added and the optimal addition rate, the target relationship can be accurately obtained.

[0080] In this embodiment, if the accuracy of the initial relationship is less than the accuracy threshold, the magnesium oxide mass interval corresponding to the initial relationship is divided; preferably, the 2-point method is used to continuously divide the magnesium oxide mass interval corresponding to the initial relationship whose accuracy is less than the accuracy threshold, until the difference between the target weights of the magnesium oxide mass of the two magnesium oxide mass intervals obtained after the last division is less than or equal to the preset difference value threshold.

[0081] As a preferred specific implementation, S474 also includes if w - 2 and w + 2 is less than or equal to the preset difference value threshold, then enter S4741.

[0082] In this embodiment, if w - 2 and w + 2 is less than or equal to the preset difference value threshold, indicating that the influence of the magnesium oxide mass on the optimal addition rate when the magnesium oxide mass is in the first sub-magnesium oxide range is consistent with the influence of the magnesium oxide mass on the optimal addition rate when the magnesium oxide mass is in the second sub-magnesium oxide range.

[0083] S4741, obtaining n3 barium carbonate mass values ​​at equal intervals from a first sub-barium carbonate mass range, and obtaining n3 barium carbonate mass values ​​at equal intervals from a second sub-barium carbonate mass range; the first sub-barium carbonate mass range is the first half of the specified barium carbonate mass range, and the second sub-barium carbonate mass range is the second half of the specified barium carbonate mass range.

[0084] In this embodiment, if the mass range of barium carbonate is specified to be 25-50 grams, then the mass range of the first sub-barium carbonate is 25-37.5 grams, and the mass range of the second sub-barium carbonate is 37.5-50 grams.

[0085] S4742, obtain the sodium oxide crystals heated to T i , the mass is M j The magnesium oxide and mass Q - k The optimal addition rate VQ of barium carbonate into sodium chloride solution - ijk , and obtain the sodium oxide crystals heated to T i , the mass is M j The magnesium oxide and mass Q + k The optimal addition rate VQ of barium carbonate into sodium chloride solution + ijk ;Q - k is the kth barium carbonate mass value obtained from the first sub-barium carbonate mass range with equal spacing, Q + k is the kth barium carbonate mass value obtained from the second sub-barium carbonate mass range with equal spacing.

[0086] Optional, VQ - ijk and VQ + ijk Obtained through experimentation, or as experience points.

[0087] S4743, according to VQ - ijk Get the target weight w of the barium carbonate mass in the first sub-barium carbonate mass range - 3, and according to VQ + ijk Get the target weight w of the barium carbonate mass in the second sub-barium carbonate mass range + 3.

[0088] In this embodiment, according to VQ - ijk Get the target weight w of the barium carbonate mass in the first sub-barium carbonate mass range - 3. Process and VQ + ijk Get the target weight w of the barium carbonate mass in the second sub-barium carbonate mass range + 3 processes are based on V ijk The process of obtaining the target weight w3 of the barium carbonate mass is similar and will not be repeated here.

[0089] S4744, if w - 3 and w + 3 is greater than the preset difference value threshold, then according to w1, w2 and w -3 Obtain the fifth sub-initial relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate, and the optimal addition rate according to w1, w2 and w + 3 Obtain a sixth sub-initial relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate.

[0090] In this embodiment, if w - 3 and w + 3 is greater than the preset difference value threshold, indicating that the influence of the barium carbonate mass in the first sub-barium carbonate mass range and the second sub-barium carbonate mass range on the optimal addition speed is different. In this case, this embodiment is based on w1, w2 and w - 3 Obtain the fifth sub-initial relationship and according to w1, w2 and w + 3 Obtain the sixth sub-initial relationship; it should be understood that the fifth sub-initial relationship characterizes the relationship between the temperature, the mass of magnesium oxide, the mass of barium carbonate in the first sub-mass range of barium carbonate, and the optimal addition rate, and the sixth sub-initial relationship characterizes the relationship between the temperature, the mass of magnesium oxide, the mass of barium carbonate in the second sub-mass range of barium carbonate, and the optimal addition rate.

[0091] S4745: If the accuracy rates of the fifth sub-initial relationship and the sixth sub-initial relationship are both greater than or equal to a preset accuracy threshold, the fifth sub-initial relationship and the sixth sub-initial relationship are determined as target relationships.

[0092] Based on S4741-S4745, in w1, w2 and w - 3 can accurately characterize the relationship between the temperature of the barium carbonate mass within the first sub-barium carbonate mass range, the mass of magnesium oxide added, the mass of barium carbonate added and the optimal addition rate, as well as w1, w2 and w + 3. When the relationship between the temperature at which the mass of barium carbonate is within the second sub-range of the mass of barium carbonate, the mass of magnesium oxide added, the mass of barium carbonate added and the optimal addition rate can be accurately characterized, the target relationship can be accurately obtained.

[0093] In this embodiment, if the accuracy of the initial relationship is less than the accuracy threshold, the barium carbonate mass interval corresponding to the initial relationship is divided; preferably, the two-point method is used to continuously divide the barium carbonate mass interval corresponding to the initial relationship whose accuracy is less than the accuracy threshold, until the difference between the target weights of the barium carbonate mass of the two barium carbonate mass intervals obtained after the last division is less than or equal to the preset difference value threshold.

[0094] In this embodiment, when the accuracy of the initial relationship is less than the accuracy threshold, the specified temperature range is first divided until the difference in the target weights of the temperatures corresponding to the two divided temperature intervals is less than or equal to the preset difference value threshold, and a new initial relationship is obtained on this basis; if the accuracy of the new initial relationship is still less than the accuracy threshold, the specified magnesium oxide mass range is divided until the difference in the target weights of the magnesium oxide masses corresponding to the two divided magnesium oxide mass intervals is less than or equal to the preset difference value threshold, and a new initial relationship is obtained on this basis; if the accuracy of the new initial relationship is still less than the accuracy threshold, the specified barium carbonate mass range is divided until the difference in the target weights of the barium carbonate masses corresponding to the two divided barium carbonate mass intervals is less than or equal to the preset difference value threshold; thereby, each relational expression constituting the target relationship can accurately characterize the relationship between the temperature within its corresponding temperature range, the magnesium oxide mass within its corresponding magnesium oxide mass range, and the barium carbonate mass within its corresponding barium carbonate mass range and the optimal addition rate.

[0095] S500, obtaining an optimal adding speed for heating the sodium oxide crystals to T' and adding magnesium oxide with a mass M' and barium carbonate with a mass B' into the sodium chloride melt according to the target relationship, the target temperature value T', the target magnesium oxide mass M' and the target barium carbonate mass B'.

[0096] In this embodiment, the target temperature value T', the target magnesium oxide mass M' and the target barium carbonate mass B' are respectively normalized and inserted into the target relationship to obtain the coefficient of the optimal addition rate, and the true value of the optimal addition rate is obtained according to the coefficient of the optimal addition rate, which is the optimal addition rate for heating the sodium oxide crystals to T' and adding magnesium oxide with a mass of M' and barium carbonate with a mass of B' to the sodium chloride melt. It should be understood that if the target relationship is composed of multiple relational expressions, and different relational expressions differ in at least one of the temperature range, magnesium oxide mass range and barium carbonate mass range, then it is determined which relational expression to substitute according to the range of the target temperature value T', the range of the target magnesium oxide mass M' and the range of the target barium carbonate mass B'.

[0097] This embodiment obtains multiple values ​​at equal intervals from a specified temperature range, magnesium oxide mass range, and barium carbonate mass range, which can fully cover the parameter range and obtain the optimal addition rate under different combinations of temperature, magnesium oxide mass, and barium carbonate mass, so as to more comprehensively understand the influence of these factors on the optimal addition rate; this embodiment simultaneously considers the influence of the three key factors of temperature, magnesium oxide mass, and barium carbonate mass on the optimal addition rate, and obtains the weights of temperature, magnesium oxide mass, and barium carbonate mass based on the optimal addition rate under the above-mentioned different combinations of temperature, magnesium oxide mass, and barium carbonate mass, and establishes the relationship between temperature, magnesium oxide mass, barium carbonate mass and the optimal addition rate. Based on this relationship, it is possible to provide operational guidance for the optimal addition rate for the preparation of zirconium oxide solid electrolyte tubes, which is beneficial to improving the conductivity, stability and other properties of the prepared zirconium oxide solid electrolyte tubes.

[0098] Although some specific embodiments of the present invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the present invention. It will also be appreciated by those skilled in the art that various modifications may be made to the embodiments without departing from the scope and spirit of the present invention. The scope of the present invention is defined by the appended claims.

Claims

1. A method for preparing a zirconium oxide solid electrolyte tube, characterized in that: The method comprises the following steps: S100, obtaining n1 temperature values ​​at equal intervals from a specified temperature range, obtaining n2 magnesium oxide mass values ​​at equal intervals from a specified magnesium oxide mass range, and obtaining n3 barium carbonate mass values ​​at equal intervals from a specified barium carbonate mass range; n1, n2 and n3 are respectively a first preset value quantity, a second preset value quantity and a third preset value quantity; S200, obtain the sodium oxide crystals heated to T i , the mass is M j The magnesium oxide and mass B k The optimal addition rate V when adding barium carbonate to sodium chloride solution ijk ; T i is the i-th temperature value obtained from the specified temperature range at equal intervals, and the value range of i is 1 to n1; M j is the jth magnesium oxide mass value obtained from the specified magnesium oxide mass range with equal spacing, and the value range of j is 1 to n2; B k is the kth barium carbonate mass value obtained from the specified barium carbonate mass range at equal intervals, and the value range of k is 1 to n3; S300, according to V ijk Obtain a target weight w1 of temperature, a target weight w2 of magnesium oxide mass, and a target weight w3 of barium carbonate mass; S400, obtaining a target relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal adding speed according to w1, w2, and w3; S500, obtaining an optimal adding speed for heating the sodium oxide crystals to T' and adding magnesium oxide with a mass M' and barium carbonate with a mass B' into the sodium chloride melt according to the target relationship, the target temperature value T', the target magnesium oxide mass M' and the target barium carbonate mass B'.

2. The method for preparing a zirconium oxide solid electrolyte tube according to claim 1, characterized in that: S300 includes: S310, obtain the mass M j The magnesium oxide and mass B k The optimal addition rate set V when adding barium carbonate to sodium chloride solution jk ; V jk = {V 1jk ,V 2jk ,…,V ijk ,…,V n1jk }; S320, according to V jk The entropy gain will be M j The magnesium oxide and mass B k The initial weight Tw of the temperature when barium carbonate is added to the sodium chloride melt jk ; S330, {Tw1, Tw2, …, Tw k ,…,Tw n3 The average initial weight of} is determined as the first specified weight Tw of temperature; Tw k is the kth subset of the initial temperature weight set, Tw k ={Tw 1,k ,Tw 2,k ,…,Tw j,k ,…,Tw n2,k }; S340, determining Tw / (Tw+Mw+Bw) as w1; Mw and Bw are the first designated weight of the mass of magnesium oxide and the first designated weight of barium carbonate, respectively.

3. The method for preparing a zirconium oxide solid electrolyte tube according to claim 1, characterized in that: S400 includes: S410, obtaining a first initial relationship of v=w1×t+w2×m+w3×b; wherein t, m and b are respectively the normalized temperature, mass of magnesium oxide and mass of barium carbonate, and v is a coefficient of an optimal adding speed obtained according to the normalized temperature, mass of magnesium oxide and mass of barium carbonate; S420, obtaining the accuracy of the first initial relationship according to a test sample set; the test sample set includes a plurality of test samples, and any test sample includes a temperature value, a mass value of magnesium oxide, a mass value of barium carbonate, and an optimal addition speed value; S430: If the accuracy of the first initial relationship is greater than or equal to a preset accuracy threshold, determine the first initial relationship as a target relationship.

4. The method for preparing a zirconium oxide solid electrolyte tube according to claim 3, characterized in that: S430 also includes: if the accuracy of the first initial relationship is less than a preset accuracy threshold, entering S440; S440, acquiring n1 temperature values ​​at equal intervals from a first sub-temperature range, and acquiring n1 temperature values ​​at equal intervals from a second sub-temperature range; the first sub-temperature range is a temperature range of the first half of the specified temperature range, and the second sub-temperature range is a temperature range of the second half of the specified temperature range; S450, obtain the sodium oxide crystals heated to C - i , the mass is M j The magnesium oxide and mass B k The optimal addition rate VC when adding barium carbonate to sodium chloride solution - ijk , and obtain the sodium oxide crystals heated to C + i , the mass is M j The magnesium oxide and mass B k The optimal addition rate VC when adding barium carbonate to sodium chloride solution + ijk ; C - i is the ith temperature value obtained from the first sub-temperature range with equal spacing, C + i is the i-th temperature value obtained from the second sub-temperature range at equal intervals; S460, according to VC - ijk Get the target weight w of the temperature in the first sub-temperature range - 1, and according to VC + ijk Get the target weight w of the temperature in the second sub-temperature range + 1; S470, if w - 1 and w + 1 is greater than the preset difference value threshold, then according to w - 1. w2 and w3 obtain the first sub-initial relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate, and according to w + 1. w2 and w3 obtain the second sub-initial relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate; S480: If the accuracy rates of the first sub-initial relationship and the second sub-initial relationship are both greater than or equal to a preset accuracy threshold, the first sub-initial relationship and the second sub-initial relationship are determined as target relationships.

5. The method for preparing a zirconium oxide solid electrolyte tube according to claim 4, characterized in that: S470 also includes: If w - 1 and w + If the difference value of 1 is less than or equal to the preset difference value threshold, the process proceeds to S471; S471, acquiring n2 magnesium oxide mass values ​​at equal intervals from a first sub-magnesium oxide mass range, and acquiring n2 magnesium oxide mass values ​​at equal intervals from a second sub-magnesium oxide mass range; the first sub-magnesium oxide mass range is the first half of the specified magnesium oxide mass range, and the second sub-magnesium oxide mass range is the second half of the specified magnesium oxide mass range; S472, obtain the sodium oxide crystals heated to T i , the mass is P - j The magnesium oxide and mass B k The optimal addition rate VP when adding barium carbonate to sodium chloride solution - ijk , and obtain the sodium oxide crystals heated to T i , the mass is P + j The magnesium oxide and mass B k The optimal addition rate VP when adding barium carbonate to sodium chloride solution + ijk ;P - j is the jth MgO mass value obtained from the first sub-MgO mass range with equal spacing, P + j is the jth MgO mass value obtained from the second sub-MgO mass range with equal spacing; S473, according to VP - ijk Get the target weight w of the magnesium oxide mass in the first sub-magnesium oxide mass range - 2, and according to VP + ijk Get the target weight w of the magnesium oxide mass in the second sub-magnesium oxide mass range + 2; S474, if w - 2 and w + 2 is greater than the preset difference value threshold, then according to w1, w - 2 and w3 obtain the third sub-initial relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added and the optimal addition rate, and according to w1, w + 2 and w3 obtain a fourth sub-initial relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate; S475: If the accuracy rates of the third sub-initial relationship and the fourth sub-initial relationship are both greater than or equal to a preset accuracy threshold, the third sub-initial relationship and the fourth sub-initial relationship are determined as target relationships.

6. The method for preparing a zirconium oxide solid electrolyte tube according to claim 4, characterized in that: S480 further includes: if the accuracy of the first sub-initial relationship is greater than or equal to a preset accuracy threshold and the accuracy of the second sub-initial relationship is less than the preset accuracy threshold, entering S481; S481, acquiring n1 temperature values ​​at equal intervals from a first sub-temperature range, and acquiring n1 temperature values ​​at equal intervals from a second sub-temperature range; the first sub-temperature range is a temperature range of the first half of the second sub-temperature range, and the second sub-temperature range is a temperature range of the second half of the second sub-temperature range; S482, obtain the sodium oxide crystals heated to C 2- i , the mass is M j The magnesium oxide and mass B k The optimal addition rate VC when adding barium carbonate to sodium chloride solution 2- ijk , and obtain the sodium oxide crystals heated to C 2+ i , the mass is M j The magnesium oxide and mass B k The optimal addition rate VC when adding barium carbonate to sodium chloride solution 2+ ijk ; C 2- i is the ith temperature value obtained from the first sub-temperature range at equal intervals, C 2+ i is the ith temperature value obtained from the second sub-temperature range at equal intervals; S483, according to VC 2- ijk Get the target weight w of the temperature in the first temperature range 2- 1, and according to VC 2+ ijk Get the target weight w of the temperature in the second temperature range 2+ 1; S484, if w 2- 1 and w 2+ 1 is greater than the preset difference value threshold, then according to w 2- 1. w2 and w3 obtain the first initial relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate, and ... 2+ 1. w2 and w3 obtain the second initial relationship between the temperature to which the sodium oxide crystals are heated, the mass of magnesium oxide added, the mass of barium carbonate added, and the optimal addition rate; S485: If the accuracy of the first sub-initial relationship and the second sub-initial relationship are both greater than or equal to a preset accuracy threshold, the first sub-initial relationship, the first sub-initial relationship and the second sub-initial relationship are determined as target relationships.

7. The method for preparing a zirconium oxide solid electrolyte tube according to claim 1, characterized in that: The mass of the sodium oxide crystals is 1000 grams, the particle size of the magnesium oxide is in the range of 50-150 nanometers, and the purity of the barium carbonate is greater than or equal to 99.5%.

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