CN116754630B - Detection device and method for electrolyte membrane for all-solid-state battery - Google Patents
Detection device and method for electrolyte membrane for all-solid-state battery Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 162
- 239000012528 membrane Substances 0.000 title claims abstract description 148
- 238000001514 detection method Methods 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims description 32
- 230000007547 defect Effects 0.000 claims abstract description 61
- 238000003825 pressing Methods 0.000 claims abstract description 51
- 239000007784 solid electrolyte Substances 0.000 claims description 34
- 229910001416 lithium ion Inorganic materials 0.000 claims description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 238000012360 testing method Methods 0.000 claims description 21
- 239000011888 foil Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 238000009831 deintercalation Methods 0.000 claims description 13
- 238000009830 intercalation Methods 0.000 claims description 13
- 230000002687 intercalation Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 11
- 230000002950 deficient Effects 0.000 claims description 11
- 229910052738 indium Inorganic materials 0.000 claims description 10
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 9
- 150000004820 halides Chemical class 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- 238000000638 solvent extraction Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 20
- 229910052744 lithium Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011532 electronic conductor Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910010629 Li6.75La3Zr1.75Nb0.25O12 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006633 Ley oxidation reaction Methods 0.000 description 1
- 229910007860 Li3.25Ge0.25P0.75S4 Inorganic materials 0.000 description 1
- 229910010787 Li6.25Al0.25La3Zr2O12 Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/4161—Systems measuring the voltage and using a constant current supply, e.g. chronopotentiometry
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a detection device and a detection method for an electrolyte membrane for an all-solid-state battery; the detection device for an electrolyte membrane for an all-solid-state battery comprises: the upper press column, the upper press plate, the potential terminal a, the electrolyte membrane to be tested, the potential terminal b, the lower press plate and the lower press column are sequentially arranged from top to bottom; the upper pressing plate of the press is provided with an upper pressing plate binding post; the lower pressing plate of the press is provided with a lower pressing plate binding post; and the sensitive voltmeter is respectively connected with the upper pressing plate binding post and the lower pressing plate binding post. The detection device can directly detect the defects of the electrolyte membrane, and after the defects exist in the detected electrolyte membrane area, the electrolyte membrane with the defects can be further detected in a partitioning mode so as to remove the defect points, and therefore recycling and reutilization of the intact area are achieved.
Description
Technical Field
The invention relates to the technical field of detection methods, in particular to a detection device and a detection method for an electrolyte membrane for an all-solid-state battery.
Background
The solid electrolyte which is nonflammable, not easy to volatilize and not flowing is used in the all-solid-state lithium ion battery to replace the electrolyte in the traditional liquid battery, so that the all-solid-state battery has more excellent safety characteristics. Meanwhile, solid electrolyte thin films are used in all-solid batteries to replace polymer separators in conventional liquid batteries. Unlike the separator in liquid battery, the solid electrolyte film is mainly composed of inorganic solid electrolyte particles and a small amount of binder, so that the lithium ion conduction function is achieved while the electron conduction between the positive electrode plate and the negative electrode plate is isolated; as shown in fig. 1.
Thus, the solid electrolyte membrane is a key component constituting the all-solid battery; if the solid electrolyte membrane is defective, the battery assembled by using the assembly becomes defective. However, there is currently no method for rapid, non-destructive inspection of electrolyte defects directly. The prior art scheme comprises:
(1) After the undetected solid electrolyte film is assembled into a battery, the internal resistance or the charge-discharge performance of the battery is tested, and then whether the electrolyte film has defects is judged. However, when the electrolyte membrane has defects, the further assembled battery cannot be used normally, and cannot be disassembled into separate components, so that the method has huge waste and risk.
(2) After the electrolyte membrane and the positive electrode tab of the solid-state battery are assembled into a composite assembly, the assembly is tested. Although the method is improved compared with the previous technical scheme, when the electrolyte membrane has defects, the composite component cannot be normally used and cannot be disassembled into separate components, and the defects of long time consumption and irrecoverability still exist.
To sum up, in the prior art, the solid electrolyte membrane and the positive electrode plate are assembled into a composite component or a complete battery for testing, so that the detection period is long and the resource waste is large; in addition, when the defect of the electrolyte membrane is found, huge time and material waste are caused, and the electrolyte membrane in the intact structure and defect-free area cannot be recycled, so that the method is a detection method for the damage of the assembly.
Disclosure of Invention
In view of the above, the present invention is directed to a device and a method for detecting an electrolyte membrane for an all-solid-state battery, which can directly detect defects on the electrolyte membrane itself, and can further detect the electrolyte membrane with defects in a partitioned manner after detecting the defects in the detected electrolyte membrane area, so as to remove the defective points, thereby realizing recycling of the intact area and truly realizing rapid and nondestructive detection.
The invention provides a detection device of electrolyte membrane for all-solid-state battery, comprising:
the upper press column, the upper press plate, the potential terminal a, the electrolyte membrane to be tested, the potential terminal b, the lower press plate and the lower press column are sequentially arranged from top to bottom; the upper press plate of the press machine is provided with an upper press plate binding post; the lower pressing plate of the press is provided with a lower pressing plate binding post;
the sensitive voltmeter is respectively connected with the upper pressing plate binding post and the lower pressing plate binding post;
the potential terminal a is M of a substance with lithium ion intercalation and deintercalation capability a A film or foil of the composition; the potential terminal b is M of a substance with lithium ion intercalation and deintercalation capability b A film or foil of the composition; the M is a And M is as follows b Different.
Preferably, said M a In, al, mg, S, coO of a shape of In, al, mg, S, coO 2 、NiO 2 、FePO 4 Or TiO 2 。
Preferably, said M b Is In 95 -Li 5 、In 9 -Li、In 4 -Li、In 7 -Li 3 、In 4.5 -Li 5.5 、In 2 -Li 3 Or In-Li.
Preferably, the electrolyte membrane to be detected is an electrolyte membrane used for an all-solid-state battery, the thickness is 5-40 mu m, and the ionic conductivity is more than 0.1mS/cm.
Preferably, the electrolyte membrane to be measured comprises inorganic solid electrolyte particles and a binder, wherein the weight percentage of the binder is less than 5wt%.
Preferably, the inorganic solid electrolyte particles are selected from one or more of oxide electrolyte particles, sulfide electrolyte particles, and halide solid electrolyte particles.
The invention also provides a detection method of the electrolyte membrane for the all-solid-state battery, which comprises the following steps:
the electrolyte membrane to be detected is arranged between the potential terminal a and the potential terminal b, and the electrolyte membrane is measured by a sensitive voltmeter after pressure is appliedTest, test result E t Comparing the corrected potential difference E, and judging whether the electrolyte membrane to be detected has defects or not;
if the defect exists, further determining a defect area by gradually shrinking the divided areas;
the defective region is removed to obtain a non-defective electrolyte membrane for an all-solid-state battery.
Preferably, the applied pressure is less than or equal to the maximum pressure that the electrolyte membrane to be measured can bear in the subsequent use process.
Preferably, the corrected potential difference e= (phi) a -φ b ）-（RT/nF）·ln（a Li /a Li+ ）；
Wherein phi is a M being a potential terminal a a Potential generated at the surface of solid electrolyte, phi b M being a potential terminal b b The potential generated on the surface of the solid electrolyte is R, T, n, F, and a.
Preferably, the step-down dividing area is specifically:
step A, reducing the sizes of a potential terminal a and a potential terminal b to 1/N of the original sizes, and determining a defect area after N times of testing, wherein N is a natural number larger than 1;
and B, repeating the step A, further testing the determined defect area, and gradually reducing the size of the defect area.
The invention provides a detection device and a detection method for an electrolyte membrane for an all-solid-state battery; the detection device comprises: the upper press column, the upper press plate, the potential terminal a, the electrolyte membrane to be tested, the potential terminal b, the lower press plate and the lower press column are sequentially arranged from top to bottom; the upper press plate of the press machine is provided with an upper press plate binding post; the lower pressing plate of the press is provided with a lower pressing plate binding post; the sensitive voltmeter is respectively connected with the upper pressing plate binding post and the lower pressing plate binding post; the potential terminal a is M of a substance with lithium ion intercalation and deintercalation capability a A film or foil of the composition; the potential terminal b is M of a substance with lithium ion intercalation and deintercalation capability b A film or foil of the composition; the M is a And M is as follows b Different. Compared with the prior art, the detection device provided by the invention adopts the structure and the connection relation, realizes better interaction, can directly detect the defects of the electrolyte membrane, and can further detect the electrolyte membrane with the defects in a partitioning manner after finding out the defects in the detected electrolyte membrane area so as to remove the defect points, thereby realizing the recovery and the reutilization of the intact area and really realizing the rapid and nondestructive detection.
In addition, the detection method of the electrolyte membrane for the all-solid-state battery has simple process steps, is easy to operate and has wide application prospect.
Drawings
Fig. 1 is a schematic view of a solid electrolyte membrane used in an all-solid battery of the prior art;
fig. 2 is a schematic structural view of a detection device for an electrolyte membrane for an all-solid battery according to an embodiment of the present invention;
fig. 3 is a schematic view of a detection area of an electrolyte membrane for an all-solid battery according to an embodiment of the present invention;
fig. 4 is a graph showing the characterization of fine pinhole defects formed in an electrolyte membrane for an all-solid-state battery.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a detection device of electrolyte membrane for all-solid-state battery, comprising:
the upper press column, the upper press plate, the potential terminal a, the electrolyte membrane to be tested, the potential terminal b, the lower press plate and the lower press column are sequentially arranged from top to bottom; the upper press plate of the press machine is provided with an upper press plate binding post; the lower pressing plate of the press is provided with a lower pressing plate binding post;
the sensitive voltmeter is respectively connected with the upper pressing plate binding post and the lower pressing plate binding post;
the potential terminal a is M of a substance with lithium ion intercalation and deintercalation capability a A film or foil of the composition; the potential terminal b is M of a substance with lithium ion intercalation and deintercalation capability b A film or foil of the composition; the M is a And M is as follows b Different.
Referring to fig. 2, fig. 2 is a schematic structural diagram of a detecting device for an electrolyte membrane for an all-solid battery according to an embodiment of the present invention; the device comprises a press upper pressing column 1, a press upper pressing plate 2, an upper pressing plate binding post 3, a potential terminal a 4, an electrolyte membrane to be tested 5, a sensitive voltmeter 6, a potential terminal b 7, a lower pressing plate binding post 8, a press lower pressing plate 9 and a press lower pressing column 10.
The invention has no special limitation on the upper pressing column of the press machine and the lower pressing column of the press machine, and can apply pressure.
In the invention, the upper press plate of the press machine is connected with an upper press column of the press machine and is provided with an upper press plate binding post; the upper pressing plate of the press is preferably an electronic conductor and is connected with one end of the sensitive voltmeter through an upper pressing plate binding post.
Likewise, the lower pressing plate of the press machine is connected with the lower pressing post of the press machine and is provided with a lower pressing plate binding post; the lower pressing plate of the press is preferably an electronic conductor and is connected with the other end of the sensitive voltmeter through a binding post of the lower pressing plate.
On the basis, when the sensitive voltmeter is in a disconnection state, an disconnection state is presented between the upper pressing plate of the press machine and the lower pressing plate of the press machine; when the sensitive voltmeter is in a working state, detection current between the upper pressing plate of the press machine and the lower pressing plate of the press machine can only flow through the sensitive voltmeter.
In the invention, the potential terminal a is arranged at the lower side of the upper pressing plate of the press; the potential terminal a is M of a substance with lithium ion intercalation and deintercalation capability a The film or foil is formed.
Likewise, the potential terminal b is arranged on the upper side of the lower pressing plate of the press; the potential terminal b is M of a substance with lithium ion intercalation and deintercalation capability b A film or foil of the composition; and said M a And M is as follows b Different.
In the present invention, the M a And M b Are self-stable materials and are thermodynamically stable with the electrolyte membrane to be tested; the M is a Preferably In, al, mg, S, coO 2 、NiO 2 、FePO 4 Or TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The M is b Preferably In 95 -Li 5 、In 9 -Li、In 4 -Li、In 7 -Li 3 、In 4.5 -Li 5.5 、In 2 -Li 3 Or In-Li; but cannot be Li (since Li and most sulfide solid state electrolytes, almost all halide electrolytes, and part of oxide electrolytes and binders are in thermodynamically unstable states, li thermodynamically unstable with the substances contained in the electrolyte thin film cannot be used as potential terminals in order to be nondestructive to the electrolyte membrane during the test and to reduce interference signals due to instability between the substances).
In the present invention, the electrolyte membrane to be measured is located between the potential terminal a and the potential terminal b.
In the present invention, the electrolyte membrane to be measured is an electrolyte membrane used for an all-solid-state battery, preferably: under the normal state and the non-failure state, the lithium ion battery has lithium ion conduction capability and electron blocking capability on the premise of not adding electrolyte, and the composition of the lithium ion battery contains lithium element; the thickness of the electrolyte membrane to be measured is preferably 5-40 mu m, and the ionic conductivity is preferably >0.1mS/cm.
In the present invention, the electrolyte membrane to be measured preferably includes inorganic solid electrolyte particles and a binder, more preferably consists of inorganic solid electrolyte particles and a binder, wherein the weight percentage of the binder is preferably less than 5wt%.
In the present invention, the inorganic solid electrolyte particles are preferably selected from the group consisting of oxide electrolyte particles, sulfide electrolyte particlesOne or more of the particles, halide solid electrolyte particles, more preferably oxide electrolyte particles, sulfide electrolyte particles or halide solid electrolyte particles; wherein the oxide electrolyte: li (Li) 3x La 2/3-x TiO 3 （0＜x≤2/3）、Li 1+ x A x B 2-x (PO 4 ) 3 (wherein A is at least one of Al, la, in, cr, ga, fe, sc, lu and Y; B is at least one of Ti, ge, zr, hf and Sn; 0.ltoreq.x.ltoreq.0.5), li 6.5 La 3 Zr 1.75 Te 0.25 O 12 、Li 6.2 Ga 0.3 La 2.95 Rb 0.05 Zr 2 O 12 、Li 6.85 La 2.9 Ca 0.1 Zr 1.75 Nb 0.25 O 12 、Li 6.25 Al 0.25 La 3 Zr 2 O 12 、Li 6.75 La 3 Zr 1.75 Nb 0.25 O 12 、Li 6.75 La 3 Zr 1.75 Nb 0.25 O 12 The method comprises the steps of carrying out a first treatment on the surface of the Sulfide electrolyte: li (Li) 3.4 Si 0.4 P 0.6 S 4 、Li 10 GeP 2 S 11.7 O 0.3 、Li 9.6 P 3 S 12 、Li 7 P 3 S 11 、Li 9 P 3 S 9 O 3 、Li 10.35 Si 1.35 P 1.65 S 12 、Li 9.81 Sn 0.81 P 2.19 S 12 、Li(Ge 0.5 Sn 0.5 )P 2 S 12 、Li 10 GeP 2 S 12 （LGPS）、Li 6 PS 5 X (wherein X is Cl, br or I), li 7 P 2 S 8 I、Li 10.35 Ge 1.35 P 1.65 S 12 、Li 3.25 Ge 0.25 P 0.75 S 4 、Li 10 SnP 2 S 12 、Li 10 SiP 2 S 12 、Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 The method comprises the steps of carrying out a first treatment on the surface of the A halide solid electrolyte: li (Li) 2 CdCl 4 、Li 2 MgCl 4 、Li 2 CdI 4 、Li 2 ZnI 4 、Li 3 OCl、LiI、Li 5 ZnI 4 、Li 3 OCl 1-x Br x (wherein 0 < x < 1).
The test principle of the invention is as follows:
since the solid electrolyte membrane itself has ion-conducting ability and electron-blocking ability, and the inorganic solid material itself constituting the electrolyte membrane is lithium-containing; therefore, the present invention utilizes the substance M used for the potential terminal having the capability of inserting and extracting lithium ions a And M is as follows b Which has a tendency to spontaneously acquire lithium ions, electrons, between a lithium-containing electrolyte membrane and the surface of a press platen having electron conductivity, and utilizes M a And M is as follows b A potential difference (E) generated by the difference in the tendency and the difficulty of acquiring lithium ions and electrons o ) And by correcting the potential difference (E) with the actual measured value (E t ) By comparing the above, it can be judged whether the electrolyte film has a local electron conduction capability (i.e., a local defect) under the tested pressure, if the electrolyte film has an electron conduction capability, E is caused t Deviating from E.
For example: m for potential terminal a a The lithium ion intercalation and deintercalation capability can be expressed as follows:
M a +nLi + +ne - =nLiM a ；
the tendency of this reaction to occur can be expressed as:
ΔG=-F φ a ；
then:
E=（φ a -φ b ）-（RT/nF）·ln（a Li /a Li+ ）；
wherein E is the corrected potential difference, phi a M being a potential terminal a a The potential generated on the surface of the solid electrolyte is R, T, n, F, and a.
Thus, it can be seen from the above formula that E is only M a 、M b Electrolytic processThe type of plasma membrane material and the temperature are related, and are irrelevant to the size, shape, thickness and pressure of the device and the electrolyte membrane to be measured (M in the invention a And M is as follows b Two different substances are necessary to produce the technical effect of the present invention, and if the same substance is used, Δg between the two substances and the electrolyte membrane is the same, that is, a measurement signal to be detected in the present invention cannot be produced).
Therefore, if the electrolyte membrane is defective, E is caused by electron conduction t If the electrolyte membrane deviates from the E, the electrolyte membrane to be tested can be judged to be defective; and further, by reducing the potential terminal in the detecting means a Potential terminal b The specific position of the defect can be further confirmed, so that the defect point can be removed by cutting on the basis, thereby reserving the qualified position and saving the cost to the greatest extent; in addition, the abnormal region can be detected by changing the shapes of the potential terminal a and the potential terminal b, and whether each position in the electrolyte membrane is qualified or not can be tested to the greatest extent.
In summary, the detection device provided by the invention adopts the structure and the connection relation, realizes better overall interaction, can directly detect the defects of the electrolyte membrane, and can further detect the electrolyte membrane with the defects in a partitioning manner after finding out the defects in the detected electrolyte membrane area so as to remove the defect points, thereby realizing recycling of the intact area and really realizing rapid and nondestructive detection.
The invention also provides a detection method of the electrolyte membrane for the all-solid-state battery, which comprises the following steps:
the electrolyte membrane detection device for the all-solid-state battery is characterized in that the electrolyte membrane to be detected is arranged between a potential terminal a and a potential terminal b, the electrolyte membrane is tested by a sensitive voltmeter after pressure is applied, and a test result E is obtained t Comparing the corrected potential difference E, and judging whether the electrolyte membrane to be detected has defects or not;
if the defect exists, further determining a defect area by gradually shrinking the divided areas;
the defective region is removed to obtain a non-defective electrolyte membrane for an all-solid-state battery.
In the present invention, the applied pressure (during the testing of the electrolyte membrane) is preferably equal to or less than the maximum pressure that the electrolyte membrane to be tested should bear during subsequent use.
In the present invention, the corrected potential difference e= (Φ) a -φ b ）-（RT/nF）·ln（a Li /a Li+ ）；
Wherein phi is a M being a potential terminal a a Potential generated at the surface of solid electrolyte, phi b M being a potential terminal b b The potential generated on the surface of the solid electrolyte is R, T, n, F, and a.
In the present invention, the manner of gradually narrowing the divided regions is preferably specifically:
step A, reducing the sizes of a potential terminal a and a potential terminal b to 1/N of the original sizes, and determining a defect area after N times of testing, wherein N is a natural number larger than 1;
and B, repeating the step A, further testing the determined defect area, and gradually reducing the size of the defect area.
The invention provides a nondestructive and rapid detection method of a solid electrolyte membrane, which is used for detecting and further removing a region with defects in the solid electrolyte membrane on the basis of the nondestructive and rapid detection method. The detection method is capable of detecting defects common to solid electrolyte membranes, which are typically generated during the preparation of the electrolyte membrane. The preparation method of the common all-solid electrolyte membrane comprises the following steps:
the binder PVDF is dissolved in the solvent NMP, and after complete dissolution, the sulfide electrolyte Li is prepared 6 PS 5 Cl according to Li 6 PS 5 Cl: PVDF mass ratio = 99:1 is added into the sol in proportion, and fully stirred to form slurry, wherein the solid content of the slurry is 55%; and coating the slurry on a substrate, and vacuum drying at 90 ℃ to prepare the electrolyte film.
Since inorganic solid particles account for a large part in the solid electrolyte membrane, the following defects easily occur in the preparation process:
(1) Pinhole: because the slurry has uneven surface tension in the drying process, shrinkage is uneven in the solvent drying process, fine pinhole defects are formed at places where inorganic particles are not covered, and the surface of the electrolyte membrane is characterized by using a Leyes Z01-3 portable digital microscope, as shown in figure 4. The presence of pinholes can increase the risk of shorting the positive and negative electrodes.
(2) Cracking: the electrolyte slurry has too high drying rate in the drying process, or the electrolyte membrane is heated unevenly up and down, so that the surface is cracked, and the existence of cracks in the electrolyte membrane can increase the risk of short circuit of the anode and the cathode.
(3) Foreign matter: the presence of foreign matter may cause the cell to crush the electrolyte membrane during subsequent pressurization, thereby causing mechanical damage and further causing shorting of the positive and negative electrodes.
The invention provides a nondestructive and rapid detection method for an electrolyte membrane, which has the following beneficial effects:
(1) The detection method provided by the invention can directly test the electrolyte membrane without assembling into a component or a complete battery and then testing; the defects and specific positions in the electrolyte membrane can be identified before further processing, and defect points can be removed on the basis;
(2) The detection method provided by the invention is nondestructive to the test of the electrolyte membrane, and the electrolyte membrane can still keep the original state after the test, so that the next processing can be carried out;
(3) The detection method provided by the invention has no requirement on the area and shape of the electrolyte membrane test area, and can infinitely subdivide the tested electrolyte membrane in the test process until the defect point of the electrolyte membrane is detected.
The invention provides a detection device and a detection method for an electrolyte membrane for an all-solid-state battery; the detection device comprises: the upper pressing column, the upper pressing plate, the potential terminal a, the electrolyte membrane to be tested, the potential terminal b, the lower pressing plate and the lower pressing plate of the press are sequentially arranged from top to bottomA column; the upper press plate of the press machine is provided with an upper press plate binding post; the lower pressing plate of the press is provided with a lower pressing plate binding post; the sensitive voltmeter is respectively connected with the upper pressing plate binding post and the lower pressing plate binding post; the potential terminal a is M of a substance with lithium ion intercalation and deintercalation capability a A film or foil of the composition; the potential terminal b is M of a substance with lithium ion intercalation and deintercalation capability b A film or foil of the composition; the M is a And M is as follows b Different. Compared with the prior art, the detection device provided by the invention adopts the structure and the connection relation, realizes better interaction, can directly detect the defects of the electrolyte membrane, and can further detect the electrolyte membrane with the defects in a partitioning manner after finding out the defects in the detected electrolyte membrane area so as to remove the defect points, thereby realizing the recovery and the reutilization of the intact area and really realizing the rapid and nondestructive detection.
In addition, the detection method of the electrolyte membrane for the all-solid-state battery has simple process steps, is easy to operate and has wide application prospect.
In order to further illustrate the present invention, the following examples are provided.
Example 1: referring to fig. 2, fig. 2 is a schematic structural diagram of a detecting device for an electrolyte membrane for an all-solid-state battery according to an embodiment of the present invention, wherein 1 is an upper press column of a press, 2 is an upper press plate of the press, 3 is an upper press plate binding post, 4 is a potential terminal a, 5 is an electrolyte membrane to be detected, 6 is a sensitive voltmeter, 7 is a potential terminal b, 8 is a lower press plate binding post, 9 is a lower press plate of the press, and 10 is a lower press column of the press.
In fig. 2, an upper press plate 2 of the press is an electronic conductor and is connected with one end of a sensitive voltmeter 6 through an upper press plate binding post 3; similarly, the press lower platen 9 is an electronic conductor, and is connected to the other end of the sensitivity voltmeter 6 via a lower platen binding post 8.
When the sensitive voltmeter 6 is in a disconnection state, an disconnection state is presented between the upper press plate 2 and the lower press plate 9; when the sensitive voltmeter 6 is in an operating state, a detection current between the press upper platen 2 and the press lower platen 9 can flow only through the sensitive voltmeter 6.
The electrolyte membrane 5 to be measured is an electrolyte membrane used for an all-solid-state battery, specifically:
from sulfide electrolyte Li 10 GeP 2 S 12 With a binder PVDF, wherein Li 10 GeP 2 S 12 98wt% and PVDF 2wt%; the electrolyte membrane has a thickness of 30 μm and an ionic conductivity of 5.7mS/cm; the electrolyte membrane has a rectangular shape with a size of 10cm×20 cm; the maximum pressure that the electrolyte membrane needs to bear in the subsequent processing process is 5MPa.
M of potential terminal a a In foil formation using In, M of potential terminal b b In-Li thin film was formed using In-Li, and tested, e= (Φ) at 25 ℃ a -φ b ）-（RT/nF）·ln（a Li /a Li+ ）=1.75V。
The working process (detection method) of the detection device of the electrolyte membrane for the all-solid-state battery provided by the embodiment of the invention is as follows:
(1) The sizes of the potential terminal a and the potential terminal b are 9.8cm multiplied by 19.8cm, the electrolyte membrane 5 to be tested is tested, and the applied pressure is 5MPa of the maximum pressure required to be born by the subsequent electrolyte membrane; e after application of pressure t =1.26V, indicating that the electrolyte membrane has defects in the area range tested.
(2) Four regions of the electrolyte membrane were further tested using the potential terminal a and the potential terminal b having dimensions of 5cm×4cm, as shown in fig. 3.
Wherein E of regions 1, 3, 4 t =1.75v=e, indicating that the above region point is acceptable; and E of zone 2 t <E, it can be determined that the region 2 has a defect.
Further, using a potential terminal a and a potential terminal b with dimensions of 2.5cm×5cm, the electrolyte membrane region 2 was further divided into four regions of regions 5, 6, 7, 8 for testing; wherein E of regions 5, 6, 8 t =1.75v=e, indicating that the above region point is acceptable; and E of region 7 t <E, it can be judged that the region 7 has a defect.
Similarly, furtherThe area 7 is further divided, and the areas 9, 10, 11, 12 are tested by using a potential terminal a and a potential terminal b with the sizes of 1.25cm multiplied by 2.5 cm; e of regions 9, 10, 12 t =1.75v=e, indicating that the above region point is acceptable; and E of region 11 t <E, it can be determined that the region 11 has a defect.
Finally, after removing the region 11, the electrolyte membrane of the remaining qualified region may be left; after the reserved qualified area is cut, the qualified area can flow into the next working procedure, and resources are saved to the greatest extent.
Example 2: the same electrolyte membrane as in example 1 was used.
M of potential terminal a a In foil formation using In, M of potential terminal b b Using In 7 -Li 3 The film formed, tested, was E= (phi) at 25 DEG C a -φ b ）-（RT/nF）·ln（a Li /a Li+ ）=1.44V。
The working process (detection method) of the detection device of the electrolyte membrane for the all-solid-state battery provided by the embodiment of the invention is as follows:
(1) The sizes of the potential terminal a and the potential terminal b are 5cm multiplied by 5cm, the electrolyte membrane to be tested is tested, the thickness of the electrolyte membrane is 40 micrometers, and the applied pressure is 3MPa which is the maximum pressure required to be born by the subsequent electrolyte membrane; e after application of pressure t =1.44v=e, indicating that the above region point is acceptable. The determination may be made to flow to the next process.
Example 3: the same electrolyte membrane as in example 1 was used.
M of potential terminal a a Formation of Mg foil using Mg, M of potential terminal b b Using In 4.5 -Li 5.5 The film formed, tested, was E= (phi) at 25 DEG C a -φ b ）-（RT/nF）·ln（a Li /a Li+ ）=0.53V。
The working process (detection method) of the detection device of the electrolyte membrane for the all-solid-state battery provided by the embodiment of the invention is as follows:
(1) The electrolyte membrane to be tested is prepared by using the dimensions of the potential terminal a and the potential terminal b which are 15cm multiplied by 15cmTesting, wherein the thickness of the electrolyte membrane is 20 micrometers, and the applied pressure is 1MPa of the maximum pressure required to be born by the subsequent electrolyte membrane; e after application of pressure t =0.53 v=e, indicating that the above area point is acceptable. The determination may be made to flow to the next process.
Example 4: the same electrolyte membrane as in example 1 was used.
M of potential terminal a a Formation of Mg foil using Mg, M of potential terminal b b Using In 4.5 -Li 5.5 The film formed, tested, was E= (phi) at 25 DEG C a -φ b ）-（RT/nF）·ln（a Li /a Li+ ）=0.53V。
The working process (detection method) of the detection device of the electrolyte membrane for the all-solid-state battery provided by the embodiment of the invention is as follows:
(1) The sizes of the potential terminal a and the potential terminal b are 15cm multiplied by 15cm, the electrolyte membrane to be tested is tested, the thickness of the electrolyte membrane is 5 micrometers, and the applied pressure is 1MPa of the maximum pressure required to be born by the subsequent electrolyte membrane; e after application of pressure t =0.11V<E, indicating that the region has defects, and the defect cannot flow into the next process, and judging after cutting or preparing again.
Example 5: the same electrolyte membrane as in example 1 was used.
M of potential terminal a a Formation of Mg foil using Mg, M of potential terminal b b Using In 4.5 -Li 5.5 The film formed, tested, was E= (phi) at 25 DEG C a -φ b ）-（RT/nF）·ln（a Li /a Li+ ）=0.53V。
The working process (detection method) of the detection device of the electrolyte membrane for the all-solid-state battery provided by the embodiment of the invention is as follows:
(1) The sizes of the potential terminal a and the potential terminal b are 15cm multiplied by 15cm, the electrolyte membrane to be tested is tested, the thickness of the electrolyte membrane is 40 micrometers, and the applied pressure is 1MPa of the maximum pressure required to be born by the subsequent electrolyte membrane; e after application of pressure t =0.53 v=e, indicating that the above area point is acceptable. The determination may be made to flow to the next process.
Comparative example 1: the detection apparatus and method provided in example 1 are employed, with the difference that: m of potential terminal b b A Li foil was used.
The results show that due to sulfide electrolyte Li 10 GeP 2 S 12 Is thermodynamically unstable to lithium metal, so at the contact interface during testing, li 10 GeP 2 S 12 Will decompose into Li 4 GeS、P、LiP 7 、Ge、Li 3 P 7 、Li 2 P、Li 3 P、LiGe、Li 9 Ge 4 、Li 15 Ge 4 . Thus, the electrolyte membrane has changed its composition after being tested, and this method is a kind of damage detection, and the electrolyte membrane after detection cannot be continued to flow into the next process for continued use.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. An apparatus for detecting an electrolyte membrane for an all-solid-state battery, comprising:
the upper press column, the upper press plate, the potential terminal a, the electrolyte membrane to be tested, the potential terminal b, the lower press plate and the lower press column are sequentially arranged from top to bottom; the upper press plate of the press machine is provided with an upper press plate binding post; the lower pressing plate of the press is provided with a lower pressing plate binding post;
the sensitive voltmeter is respectively connected with the upper pressing plate binding post and the lower pressing plate binding post;
the potential terminal a is M of a substance with lithium ion intercalation and deintercalation capability a A film or foil of the composition; the M is a Is In, al, mg or S; the potential terminal bM being a substance having lithium ion intercalation and deintercalation ability b A film or foil of the composition; the M is b Is In 95 -Li 5 、In 9 -Li、In 4 -Li、In 7 -Li 3 、In 4.5 -Li 5.5 、In 2 -Li 3 Or In-Li; the M is a And M is as follows b Different.
2. The apparatus according to claim 1, wherein the electrolyte membrane to be measured is an electrolyte membrane used for an all-solid-state battery, and has a thickness of 5 to 40 μm and an ion conductivity of >0.1mS/cm.
3. The apparatus for detecting an electrolyte membrane for an all-solid battery according to claim 1, wherein the electrolyte membrane to be detected comprises inorganic solid electrolyte particles and a binder, wherein the weight percentage of the binder is less than 5wt%.
4. The apparatus for detecting an electrolyte membrane for an all-solid battery according to claim 3, wherein the inorganic solid electrolyte particles are one or more selected from the group consisting of oxide electrolyte particles, sulfide electrolyte particles, and halide solid electrolyte particles.
5. A method for detecting an electrolyte membrane for an all-solid-state battery, comprising the steps of:
a detection device for an electrolyte membrane for an all-solid-state battery according to any one of claims 1 to 4, wherein the electrolyte membrane to be detected is placed between a potential terminal a and a potential terminal b, and after pressure is applied, the electrolyte membrane is tested by a sensitive voltmeter, and the test result E is obtained t Comparing the corrected potential difference E, and judging whether the electrolyte membrane to be detected has defects or not; the corrected potential difference E= (phi) a -φ b ）-（RT/nF）·ln（a Li /a Li+ ）；
Wherein phi is a M being a potential terminal a a Potential generated at the surface of solid electrolyte, phi b M being a potential terminal b b The potential generated on the surface of the solid electrolyte is that R is a gas constant, T is a temperature, n is an electron number, F is a Faraday constant, and a is an activity;
if the defect exists, further determining a defect area by gradually shrinking the divided areas; the mode of gradually shrinking the divided areas is as follows: the specific position of the defect is further confirmed by reducing the areas of the potential terminal a and the potential terminal b in the detection device;
the defective region is removed to obtain a non-defective electrolyte membrane for an all-solid-state battery.
6. The method according to claim 5, wherein the applied pressure is equal to or less than a maximum pressure that the electrolyte membrane to be measured is required to bear in a subsequent use process.
7. The method for detecting an electrolyte membrane for an all-solid battery according to claim 5, wherein the manner of gradually narrowing the divided regions is specifically:
step A, reducing the sizes of a potential terminal a and a potential terminal b to 1/N of the original sizes, and determining a defect area after N times of testing, wherein N is a natural number larger than 1;
and B, repeating the step A, further testing the determined defect area, and gradually reducing the size of the defect area.
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