CN113782823B - Preparation method of lithium supplementing functional electrolyte membrane for solid-state lithium battery - Google Patents

Preparation method of lithium supplementing functional electrolyte membrane for solid-state lithium battery Download PDF

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CN113782823B
CN113782823B CN202110922619.8A CN202110922619A CN113782823B CN 113782823 B CN113782823 B CN 113782823B CN 202110922619 A CN202110922619 A CN 202110922619A CN 113782823 B CN113782823 B CN 113782823B
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lithium
inorganic solid
solid electrolyte
dispersion liquid
supplementing
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CN113782823A (en
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林久
许晓雄
杨杰
楼凯
崔言明
张永龙
戈志敏
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Zhejiang Funlithium New Energy Tech Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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    • H—ELECTRICITY
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    • H01—ELECTRIC ELEMENTS
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Abstract

The invention discloses a preparation method of a lithium supplementing functional electrolyte membrane for a solid-state lithium battery, which comprises the following steps: s1, respectively dispersing a lithium-containing compound and an inorganic solid electrolyte in NMP to prepare a lithium-containing compound dispersion liquid and an inorganic solid electrolyte dispersion liquid; stirring and dissolving a binder in NMP to prepare a binder solution; s2, mixing the lithium-containing compound dispersion liquid and the inorganic solid electrolyte dispersion liquid according to the mass ratio, and adding a conductive agent into the mixture to prepare a mixed dispersion liquid; s3, adding the binder solution obtained in the step S1 into the mixed dispersion liquid obtained in the step S2, and performing ball milling and mixing to obtain uniform slurry; and S4, coating the uniform slurry on the surface of one side opposite to the reinforcing layer and the framework layer through a double unreeling mode, and drying in an oven of a coating machine to form a lithium supplementing electrolyte layer between the reinforcing layer and the framework layer, thereby obtaining the lithium supplementing functional electrolyte membrane for the solid-state lithium battery. The cycle performance of the prepared electrolyte membrane 1C is improved by more than 50 percent.

Description

Preparation method of lithium supplementing functional electrolyte membrane for solid-state lithium battery
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a preparation method of a lithium-supplementing functional electrolyte membrane for a solid-state lithium battery.
Background
The lithium ion battery has the advantages of higher energy density, long cycle life and the like, and is widely applied to the fields of portable electronic products, electric automobiles and the like. In the first charging process of a lithium ion battery, an SEI film is formed on the surface of the negative electrode, which consumes active lithium in the positive electrode, resulting in irreversible capacity loss, the irreversible capacity loss of the graphite negative electrode which is most widely used at present can reach 10%, and for silicon-based and tin-based negative electrodes with high specific capacities, the irreversible capacity loss is even higher than 30%, which greatly reduces the energy density of the lithium ion battery. For the problem, at present, the irreversible loss of lithium ions is compensated by a lithium supplementing method in academia and industry, so that the capacity of the positive electrode can be recovered, and the energy density of the lithium ion battery is greatly improved.
From the technical path, the currently mainstream lithium supplementing schemes can be divided into three main categories: 1) The negative electrode lithium supplement is mainly inert metal lithium powder, metal lithium foil and vacuum winding evaporation plating lithium supplement; 2) Positive electrode lithium-supplementing, mainly of oxides containing lithium, e.g. Li 5 FeO 4 Etc.; 3) The third electrode supplements lithium by charging and discharging between the negative electrode and the third electrode (for example, a metal lithium electrode and a high-capacity lithium-containing oxide electrode).
The negative electrode adopts the metal lithium to supplement lithium, has the advantages of high lithium supplementing efficiency, no residue after reaction, high activity of the metal lithium, high requirement on environmental control, large equipment, large cost investment and large influence on the existing production process. Meanwhile, the adoption of the metal lithium also has a large safety risk, and particularly, the metal lithium powder can cause risks of dust explosion and the like when suspended in the air. Meanwhile, if the lithium supplement is insufficient, the energy density is not obviously improved; excessive lithium supplementation can form a metal lithium coating on the surface of the negative electrode, and the battery performance is damaged.
The positive electrode lithium supplement has the advantages of simple process, low cost, high safety and the like, and has received a great deal of attention in recent years. Patent CN110120493a provides a positive electrode lithium supplementing method of pulping and smearing a lithium supplementing material together with a positive electrode material, a conductive agent and a binder, but in this method, the lithium supplementing sacrificial agent has a certain influence on mass transfer inside the whole pole piece after delithiation of the positive electrode side. Patent CN109755448A will contain Li 5 FeO 4 Coating lithium supplementing coating of lithium containing compound, nano inert inorganic filler and binder on diaphragm base material to prepare lithium battery with lithium supplementing coatingThe separator reduces the heat shrinkage of the separator while supplementing lithium, but after lithium is removed from the separator by the lithium supplementing agent, the adhesion between the lithium supplementing layer and the separator base material may be affected, and the lithium supplementing agent falls into the electrolyte, so that the lithium supplementing efficiency is reduced.
Therefore, the electrolyte membrane with the lithium supplementing function for the solid-state lithium battery, which has the high-efficiency controllable lithium supplementing effect, can prolong the cycle life of the battery and has better temperature resistance, is particularly important for the development of the lithium battery.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium-supplementing functional electrolyte membrane for a solid-state lithium battery, which can effectively solve the problems that a lithium-supplementing diaphragm in the prior art is poor in temperature resistance and a lithium-supplementing layer can fall into electrolyte.
The technical scheme adopted for solving the technical problems is as follows:
a preparation method of a lithium supplementing functional electrolyte membrane for a solid lithium battery comprises the following specific steps:
s1, respectively weighing a lithium-containing compound, an inorganic solid electrolyte, a binder and a conductive agent, respectively dispersing the weighed lithium-containing compound and inorganic solid electrolyte in NMP, and respectively ball-milling to prepare a lithium-containing compound dispersion liquid and an inorganic solid electrolyte dispersion liquid; simultaneously stirring and dissolving the weighed binder in NMP to prepare a binder solution;
s2, mixing the lithium-containing compound dispersion liquid and the inorganic solid electrolyte dispersion liquid according to the mass ratio, adding a conductive agent into the mixture, and continuing ball milling, dispersing and mixing to prepare a mixed dispersion liquid;
s3, adding the binder solution obtained in the step S1 into the mixed dispersion liquid obtained in the step S2, and performing ball milling and mixing to obtain uniform slurry;
and S4, coating the uniform slurry obtained in the step S3 on the surface of one side of the reinforcing layer opposite to the skeleton layer through a double unreeling mode, drying in an oven of a coating machine, and further forming a lithium supplementing electrolyte layer between the reinforcing layer and the skeleton layer, thereby obtaining the lithium supplementing functional electrolyte membrane for the solid-state lithium battery.
Preferably, the lithium-supplementing electrolyte layer obtained in the step S4 contains 10% to 45% of lithium compound, the inorganic solid electrolyte particles 50% to 80%, the binder 3.5% to 10%, and the conductive agent 0.5% to 2%.
Preferably, in the step S1, the binder is dissolved in NMP with stirring at a solid content of 10% to prepare a binder solution.
Preferably, the particle diameter of the lithium-containing compound after ball milling in the step S1 is 0.1 μm to 2. Mu.m.
Preferably, the particle size of the inorganic solid electrolyte after ball milling in the step S1 is 0.1 μm to 2. Mu.m.
Preferably, the lithium-containing compound in the step S1 includes at least one of lithium iron oxide, lithium nickel oxide, lithium cobalt oxide, organic lithium salt, lithium oxide, lithium sulfide, lithium phosphide, and lithium nitride.
Preferably, the lithium-containing compound in the step S1 is Li 5 FeO 4 、Li 5 Fe 5 O 8 、Li 6 CoO 4 、 Li 2 NiO 2 、Li 2 O、Li 2 S、Li 3 P、Li 3 N、Li 2 O 2 、Li 2 C 2 O 4 、Li 2 At least one of DHBN
Preferably, the inorganic solid electrolyte particles in step S1 have a NASICON structure, and the chemical formula of the inorganic solid electrolyte particles is LiM 2 (PO 4 ) 3 、Li 1+x Al x Ti 2-x (PO 4 ) 3 And Li (lithium) 1+x Al x Ge 2-x (PO 4 ) 3 Wherein M is one of Ti, ge and Hf, and x is more than 0 and less than 2;
or the inorganic solid electrolyte particles are of perovskite structure, and the chemical formula of the inorganic solid electrolyte particles is Li 0.34 La 0.56 TiO 3 And/or Li 0.5 La 0.5 TiO 3 ；
Or a instituteThe inorganic solid electrolyte particles are of LISICON structure, and the chemical formula of the inorganic solid electrolyte particles is Li 14 Zn(GeO 4 ) 4 ；
Or the inorganic solid electrolyte particles are garnet-type structures, and the chemical formula of the inorganic solid electrolyte particles is Li 5 La 3 R 2 O 12 、Li 6 ALa 2 R 2 O 12 、Li 5.5 La 3 R 1.75 D 0.25 O 12 、Li 7 La 3 Zr 2 O 12 And Li (lithium) 7.06 E 3 Y 0.06 Zr 1.94 O 12 Wherein R is Nb or Ta, A is one of Ca, sr and Ba, D is In or Zr, and E is one of La, nb and Ta;
or the inorganic solid electrolyte particles are of an inverse perovskite structure, and the chemical formula of the inorganic solid electrolyte particles is Li 3 OX, wherein X is one of F, cl and Br;
or the inorganic solid electrolyte particles are in a glass state or a glass ceramic state, and the inorganic solid electrolyte particles are sulfide Li 10 GeP 2 S 12 、Li 2 S-SiS 2 、Li 2 S-P 2 S 5 、 70Li 2 S-30P 2 S 5 One or more of the following.
Preferably, the binder in the step S1 is at least one of PVDF and PVDF-HFP, PVP, PEO, PAN, EVA, PMMA;
the conductive agent in the step S2 is one or more of Super-P, ketjen black, CNTs and graphene;
the skeleton layer in the step S4 is a three-dimensional porous structure nonwoven film, and comprises a first polymer base material, wherein the first polymer base material is one of cellulose and PET, PI, PVDF, PA, PVC;
the reinforcing layer in the step S4 includes a second polymer base material, and the second polymer base material is one of PE, PP, and PE/PP/PE.
Preferably, the temperature of the oven in the step S4 is 60 to 80 ℃.
Compared with the prior art, the preparation method of the lithium-supplementing functional electrolyte membrane for the solid-state lithium battery can prepare the lithium-supplementing functional electrolyte membrane for the solid-state lithium battery, and the lithium-containing compound in the electrolyte membrane can take off more lithium ions to participate in forming an SEI layer in the battery charging process, so that the loss of the lithium ions in the positive electrode active material is reduced, more lithium ions can participate in the intercalation and the deintercalation, the discharge capacity of the lithium battery is improved, and the charge-discharge cycle life of the lithium battery can be prolonged; the electrolyte membrane prepared by the method has obviously improved safety performance and can pass a needling test.
Drawings
FIG. 1 is an electron micrograph of the surface of a lithium-compensating electrolyte layer in this example;
fig. 2 is a cycle life curve of the present embodiment in the 1C (1c=5a) charge/discharge mode;
FIG. 3 is a photograph (from top to bottom, example 1, comparative example 1 and comparative example 2, respectively) of the present example before heat treatment at 180 ℃;
FIG. 4 is a photograph (from top to bottom, example 1, comparative example 1 and comparative example 2, respectively) of the present example after heat treatment at 180℃for 1 hour.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
The electrolyte membrane is composed of a framework layer, a reinforcing layer and a lithium supplementing electrolyte layer positioned between the framework layer and the reinforcing layer, wherein the framework layer is provided with a three-dimensional porous structure, and part of the lithium supplementing electrolyte layer is filled in the porous structure of the framework layer.
Lithium ions are extracted from the lithium supplementing electrolyte layer in the charging and discharging process of the battery, the lithium supplementing electrolyte layer participates in forming an SEI layer, the loss of lithium ions in an anode active substance is further reduced, and the lithium supplementing electrolyte layer is arranged between the framework layer and the reinforcing layer, so that the structure of the lithium supplementing electrolyte layer is changed even if the lithium supplementing electrolyte layer is subjected to lithium extraction in the lithium supplementing process, the lithium supplementing electrolyte layer cannot fall into electrolyte due to the falling of the lithium supplementing electrolyte layer, and the lithium supplementing effect is further ensured.
And the reinforcing layer is arranged, so that the overall mechanical strength of the film is higher. Experiments find that, an inorganic electrolyte layer is arranged on one side of a framework layer, a composite electrolyte layer is arranged on the other side of the framework layer, the mechanical strength of a lithium-supplementing electrolyte film obtained by the composite electrolyte layer is only 50Mpa at most, the lithium-supplementing electrolyte layer of the lithium-supplementing functional electrolyte film for the solid-state lithium battery in the embodiment is filled in the framework layer and between the framework layer and a reinforcing layer, the framework layer and the reinforcing layer are tightly adhered through the lithium-supplementing electrolyte layer, and the integral mechanical strength of the film is greater than 100Mpa, so that the integral film can meet the strength specification of equipment pulling in the manufacturing process of a battery core, and meanwhile, the test of the safety performance such as heavy-load impact resistance of a subsequent battery core is met.
Specifically, the lithium-compensating electrolyte layer includes a lithium-containing compound, inorganic solid electrolyte particles, a binder, and a conductive agent.
The lithium-containing compound in the lithium-supplementing functional electrolyte membrane for the solid-state lithium battery can take off more lithium ions in the battery charging process, participate in forming an SEI layer, further reduce the loss of the lithium ions in the positive electrode active substance, further ensure that more lithium ions participate in the intercalation and the deintercalation, improve the discharge capacity of the lithium battery and prolong the charge-discharge cycle life of the lithium battery.
The content of the lithium-containing compound is 10% -45%, the content of the inorganic solid electrolyte particles is 50% -80%, the content of the binder is 3.5% -10%, and the content of the conductive agent is 0.5% -2%.
The lithium-containing compound is a lithium-containing compound having a high irreversible capacity in a certain voltage range, and includes at least one of lithium iron oxide, lithium nickel oxide, lithium cobalt oxide, organic lithium salt, lithium oxide, lithium sulfide, lithium phosphide, and lithium nitride.
Specifically, the lithium-containing compound is Li 5 FeO 4 、Li 5 Fe 5 O 8 、Li 6 CoO 4 、Li 2 NiO 2 、Li 2 O、 Li 2 S、Li 3 P、Li 3 N、Li 2 O 2 、Li 2 C 2 O 4 、Li 2 At least one of DHBN.
The activity of the lithium-containing compound increases with decreasing particle size, and is more reactive with environmental moisture, binders and solutions, accelerating the slurry gel. The lithium-containing compound with large particles has poor dynamic and causes the lithium supplementing efficiency to be reduced, so that the particle size of the lithium-containing compound needs to be moderate, and the particle size of the lithium-containing compound is preferably 0.1-2 mu m, thereby being beneficial to improving the exertion of the lithium supplementing efficiency while improving the stability of the slurry and further improving the energy density and the electrochemical performance of the battery.
The inorganic solid electrolyte particles are of a NASICON structure, and the chemical formula of the inorganic solid electrolyte particles is LiM 2 (PO 4 ) 3 、Li 1+x Al x Ti 2-x (PO 4 ) 3 (LATP) and Li 1+x Al x Ge 2-x (PO 4 ) 3 (LAGP) wherein M is one of Ti, ge and Hf, 0 < x < 2;
or the inorganic solid electrolyte particles are of perovskite structure, and the chemical formula of the inorganic solid electrolyte particles is Li 0.34 La 0.56 TiO 3 And/or Li 0.5 La 0.5 TiO 3 ；
Or the inorganic solid electrolyte particles are of LISICON structure, and the chemical formula of the inorganic solid electrolyte particles is Li 14 Zn(GeO 4 ) 4 ；
Or the inorganic solid electrolyte particles are of garnet structure, and the chemical formula of the inorganic solid electrolyte particles is Li 5 La 3 R 2 O 12 、Li 6 ALa 2 R 2 O 12 、Li 5.5 La 3 R 1.75 D 0.25 O 12 、Li 7 La 3 Zr 2 O 12 And Li (lithium) 7.06 E 3 Y 0.06 Zr 1.94 O 12 Wherein R is Nb or Ta, A is one of Ca, sr and Ba, D is In or Zr, and E is one of La, nb and Ta;
or inorganicThe solid electrolyte particles are of an inverse perovskite structure, and the chemical formula of the inorganic solid electrolyte particles is Li 3 OX, X is one of F, cl and Br;
or the inorganic solid electrolyte particles are in a glass state or a glass ceramic state, and the inorganic solid electrolyte particles are sulfide Li 10 GeP 2 S 12 、Li 2 S-SiS 2 、Li 2 S-P 2 S 5 、70Li 2 S-30P 2 S 5 One or more of the following.
The particle size of the inorganic solid electrolyte particles is 0.1-2 μm so as to be matched with the particle size of the lithium-containing compound and facilitate coating.
The binder is at least one of PVDF and PVDF-HFP, PVP, PEO, PAN, EVA, PMMA.
The conductive agent is one or more of Super-P, ketjen black, CNTs and graphene.
The skeleton layer is a three-dimensional porous structure nonwoven film, and comprises a first polymer base material, wherein the first polymer base material is one of cellulose and PET, PI, PVDF, PA, PVC.
The reinforcing layer comprises a second polymer substrate, and the second polymer substrate is one of PE, PP and PE/PP/PE.
Compared with the prior art, the lithium-supplementing functional electrolyte membrane for the solid-state lithium battery has the advantages that the lithium-containing compound in the lithium-supplementing functional electrolyte membrane for the solid-state lithium battery can be used for removing and inserting more lithium ions in the battery charging process to participate in forming an SEI layer, so that the loss of the lithium ions in the positive electrode active material is reduced, more lithium ions can be ensured to participate in and remove from the electrolyte membrane, the discharge capacity of the lithium battery is improved, and the charge-discharge cycle life of the lithium battery is prolonged.
The lithium supplementing electrolyte layer is filled in the framework layer and between the framework layer and the reinforcing layer, and the framework layer and the reinforcing layer are tightly adhered through the lithium supplementing electrolyte layer, so that good lithium supplementing can be realized, and the problem that the lithium supplementing effect is affected due to the fact that the electrolyte layer falls into the electrolyte due to the fact that the lithium supplementing agent is separated in the lithium supplementing process can be avoided; the setting of enhancement layer makes the whole mechanical strength of membrane be greater than only having the skeleton layer and sets up the membrane structure of mending lithium electrolyte layer in skeleton layer one side to guarantee in electric core manufacturing process, whole membrane can satisfy the intensity specification of equipment pulling, satisfies the test of the security performance such as heavy object impact of follow-up electric core simultaneously.
The heat resistance of the electrolyte membrane is improved through the synergistic effect of the framework layer, the reinforcing layer and the lithium supplementing electrolyte layer, the thermal shrinkage and the thermal puncture are reduced, and the safety problem caused by puncture or thermal runaway is prevented. And the inorganic solid electrolyte has higher ionic conductivity, so that the rate performance of the battery can be greatly improved.
A preparation method of a lithium supplementing functional electrolyte membrane for a solid lithium battery comprises the following specific steps:
s1, respectively weighing a lithium-containing compound, an inorganic solid electrolyte, a binder and a conductive agent, respectively dispersing the weighed lithium-containing compound and inorganic solid electrolyte in NMP, and respectively ball-milling to prepare a lithium-containing compound dispersion liquid and an inorganic solid electrolyte dispersion liquid; simultaneously stirring and dissolving the weighed binder in NMP to prepare a binder solution;
s2, mixing the lithium-containing compound dispersion liquid and the inorganic solid electrolyte dispersion liquid according to the mass ratio, adding a conductive agent into the mixture, and continuing ball milling, dispersing and mixing to prepare a mixed dispersion liquid;
s3, adding the binder solution obtained in the step S1 into the mixed dispersion liquid obtained in the step S2, and performing ball milling and mixing to obtain uniform slurry;
and S4, coating the uniform slurry obtained in the step S3 on the surface of one side of the reinforcing layer opposite to the skeleton layer through a double unreeling mode, drying in an oven of a coating machine, and further forming a lithium supplementing electrolyte layer between the reinforcing layer and the skeleton layer, thereby obtaining the lithium supplementing functional electrolyte membrane for the solid-state lithium battery.
Specifically, in step S1, a binder solution was prepared by dissolving a binder in NMP with stirring at a solid content of 10%. The particle size of the lithium-containing compound after ball milling in the step S1 is 0.1-2 mu m, and the particle size of the inorganic solid electrolyte particles after ball milling in the step S1 is 0.1-2 mu m.
The temperature of the oven in the step S4 is 60-80 ℃, the content of the lithium-containing compound in the lithium-supplementing electrolyte layer obtained in the step S4 is 10-45%, the content of the inorganic solid electrolyte particles is 50-80%, the content of the binder is 3.5-10%, and the content of the conductive agent is 0.5-2%.
The dispersing and ball milling equipment in the steps S1, S2 and S3 comprises a double-planetary dispersing machine, a planetary ball mill and a horizontal ball mill.
Example 1,
A preparation method of a lithium supplementing functional electrolyte membrane for a solid lithium battery comprises the following specific steps:
s1, respectively weighing Li 2 NiO 2 LATP, PVP and Super-P, li to be weighed 2 NiO 2 And LATP are respectively dispersed in NMP according to the solid content of 45 percent, and are respectively ball-milled to prepare lithium-containing compound dispersion liquid and inorganic solid electrolyte dispersion liquid, wherein the ball-milling speed is 300rpm, so that Li in the lithium-containing compound dispersion liquid 2 NiO 2 Particle diameter range is 0.8 μm, so that the particle diameter of LATP in the inorganic solid electrolyte dispersion is 0.3 μm; simultaneously stirring and dissolving the weighed binder in NMP to prepare a binder solution;
s2, mixing the lithium-containing compound dispersion liquid and the inorganic solid electrolyte dispersion liquid according to the mass ratio, adding a conductive agent into the mixture, and continuing ball milling and dispersing, mixing to prepare a mixed dispersion liquid, wherein the ball milling rotating speed is 300rpm, and the ball milling time is 1h;
s3, adding the binder solution obtained in the step S1 into the mixed dispersion liquid obtained in the step S2, and performing ball milling and mixing to obtain uniform slurry, wherein the ball milling rotating speed is 300rpm;
and S4, coating the uniform slurry obtained in the step S3 on the surface of one side of the reinforcing layer opposite to the framework layer through a double unreeling mode, drying in an oven of a coating machine at 60-80 ℃, and further forming a lithium supplementing electrolyte layer between the reinforcing layer and the framework layer, thereby obtaining the lithium supplementing functional electrolyte membrane for the solid-state lithium battery. Wherein the first polymer base material of the framework layer is PET, the second polymer base material of the reinforcing layer is PE, and the preparation method comprises the following steps ofLi in the obtained lithium-supplementing electrolyte layer 2 NiO 2 The LATP, PVP and Super-P contents were 30%, 64.5%, 4% and 1.5%, respectively.
EXAMPLE 2,
A preparation method of a lithium supplementing functional electrolyte membrane for a solid lithium battery comprises the following specific steps:
s1, respectively weighing Li 5 FeO 4 LLZTO, PVDF and Super-P/CNTs, li to be weighed 5 FeO 4 And LLZTO are respectively dispersed in NMP according to the solid content of 45 percent, and are respectively ball-milled to prepare lithium-containing compound dispersion liquid and inorganic solid electrolyte dispersion liquid, wherein the ball-milling speed is 300rpm, so that Li in the lithium-containing compound dispersion liquid 5 FeO 4 The particle size range is 0.1 μm, so that the particle size of LLZTO in the inorganic solid electrolyte dispersion is 0.3 μm; simultaneously stirring and dissolving the weighed binder in NMP to prepare a binder solution;
s2, mixing the lithium-containing compound dispersion liquid and the inorganic solid electrolyte dispersion liquid according to the mass ratio, adding a conductive agent into the mixture, and continuing ball milling and dispersing, mixing to prepare a mixed dispersion liquid, wherein the ball milling rotating speed is 300rpm, and the ball milling time is 1h;
s3, adding the binder solution obtained in the step S1 into the mixed dispersion liquid obtained in the step S2, and performing ball milling and mixing to obtain uniform slurry, wherein the ball milling rotating speed is 300rpm;
and S4, coating the uniform slurry obtained in the step S3 on the surface of one side of the reinforcing layer opposite to the framework layer through a double unreeling mode, drying in an oven of a coating machine at 60-80 ℃, and further forming a lithium supplementing electrolyte layer between the reinforcing layer and the framework layer, thereby obtaining the lithium supplementing functional electrolyte membrane for the solid-state lithium battery. Wherein the first polymer base material of the framework layer is PI, the second polymer base material of the reinforcing layer is PE, and Li in the prepared lithium supplementing electrolyte layer 5 FeO 4 The LLZTO, PVDF and Super-P/CNTs contents were 20%, 73.5%, 5% and 1.5%, respectively.
EXAMPLE 3,
A preparation method of a lithium supplementing functional electrolyte membrane for a solid lithium battery comprises the following specific steps:
s1, respectively weighing Li 2 DHBN, LLZNO, PVDF-HFP and graphene/CNTs, li to be weighed 2 Respectively dispersing DHBN and LLZNO in NMP according to solid content of 45%, respectively ball-milling to obtain lithium-containing compound dispersion liquid and inorganic solid electrolyte dispersion liquid, and ball-milling at 300rpm to obtain Li in the lithium-containing compound dispersion liquid 2 The DHBN particle size range is 0.3 μm, so that the particle size of LLZNO in the inorganic solid electrolyte dispersion is 0.8 μm; simultaneously stirring and dissolving the weighed binder in NMP to prepare a binder solution;
s2, mixing the lithium-containing compound dispersion liquid and the inorganic solid electrolyte dispersion liquid according to the mass ratio, adding a conductive agent into the mixture, and continuing ball milling and dispersing, mixing to prepare a mixed dispersion liquid, wherein the ball milling rotating speed is 300rpm, and the ball milling time is 1h;
s3, adding the binder solution obtained in the step S1 into the mixed dispersion liquid obtained in the step S2, and performing ball milling and mixing to obtain uniform slurry, wherein the ball milling rotating speed is 300rpm;
and S4, coating the uniform slurry obtained in the step S3 on the surface of one side of the reinforcing layer opposite to the framework layer through a double unreeling mode, drying in an oven of a coating machine at 60-80 ℃, and further forming a lithium supplementing electrolyte layer between the reinforcing layer and the framework layer, thereby obtaining the lithium supplementing functional electrolyte membrane for the solid-state lithium battery. Wherein the first polymer base material of the framework layer is cellulose, the second polymer base material of the reinforcing layer is PE, and Li in the prepared lithium supplementing electrolyte layer 2 The contents of DHBN, LLZNO, PVDF-HFP and graphene/CNTs were 40%, 52.2%, 7% and 0.8%, respectively.
EXAMPLE 4,
A preparation method of a lithium supplementing functional electrolyte membrane for a solid lithium battery comprises the following specific steps:
s1, respectively weighing Li 6 CoO 4 LAGP, EAV and CNTs, li to be weighed 6 CoO 4 Respectively dispersing LAGP in NMP according to solid content of 45%, respectively ball-milling to obtain lithium-containing compound dispersion liquid and inorganic solid electrolyte dispersion liquid, and ball-milling at 300rpm to obtain lithium-containing compound dispersion liquidLi in Compound Dispersion 6 CoO 4 The particle size range is 1.5 mu m, so that the particle size of LAGP in the inorganic solid electrolyte dispersion liquid is 0.6 mu m; simultaneously stirring and dissolving the weighed binder in NMP to prepare a binder solution;
s2, mixing the lithium-containing compound dispersion liquid and the inorganic solid electrolyte dispersion liquid according to the mass ratio, adding a conductive agent into the mixture, and continuing ball milling and dispersing, mixing to prepare a mixed dispersion liquid, wherein the ball milling rotating speed is 300rpm, and the ball milling time is 1h;
s3, adding the binder solution obtained in the step S1 into the mixed dispersion liquid obtained in the step S2, and performing ball milling and mixing to obtain uniform slurry, wherein the ball milling rotating speed is 300rpm;
and S4, coating the uniform slurry obtained in the step S3 on the surface of one side of the reinforcing layer opposite to the framework layer through a double unreeling mode, drying in an oven of a coating machine at 60-80 ℃, and further forming a lithium supplementing electrolyte layer between the reinforcing layer and the framework layer, thereby obtaining the lithium supplementing functional electrolyte membrane for the solid-state lithium battery. Wherein the first polymer base material of the framework layer is PA, the second polymer base material of the reinforcing layer is PP, and Li in the prepared lithium supplementing electrolyte layer 6 CoO 4 The LAGP, EAV and CNTs content was 15%, 78%, 6% and 1%, respectively.
EXAMPLE 5,
A preparation method of a lithium supplementing functional electrolyte membrane for a solid lithium battery comprises the following specific steps:
s1, respectively weighing Li 2 C 2 O 4 LLTO, PAN and graphene/CNTs, li to be weighed 2 C 2 O 4 And LLTO are respectively dispersed in NMP according to the solid content of 45 percent, and are respectively ball-milled to prepare a lithium-containing compound dispersion liquid and an inorganic solid electrolyte dispersion liquid, wherein the ball-milling speed is 300rpm, so that Li in the lithium-containing compound dispersion liquid 2 C 2 O 4 The particle size range was 1.5. Mu.m, so that the particle size of LLTO in the inorganic solid electrolyte dispersion was 0.6. Mu.m; simultaneously stirring and dissolving the weighed binder in NMP to prepare a binder solution;
s2, mixing the lithium-containing compound dispersion liquid and the inorganic solid electrolyte dispersion liquid according to the mass ratio, adding a conductive agent into the mixture, and continuing ball milling and dispersing, mixing to prepare a mixed dispersion liquid, wherein the ball milling rotating speed is 300rpm, and the ball milling time is 1h;
s3, adding the binder solution obtained in the step S1 into the mixed dispersion liquid obtained in the step S2, and performing ball milling and mixing to obtain uniform slurry, wherein the ball milling rotating speed is 300rpm;
and S4, coating the uniform slurry obtained in the step S3 on the surface of one side of the reinforcing layer opposite to the framework layer through a double unreeling mode, drying in an oven of a coating machine at 60-80 ℃, and further forming a lithium supplementing electrolyte layer between the reinforcing layer and the framework layer, thereby obtaining the lithium supplementing functional electrolyte membrane for the solid-state lithium battery. Wherein the first polymer base material of the framework layer is PET, the second polymer base material of the reinforcing layer is PP, and Li in the prepared lithium supplementing electrolyte layer 2 C 2 O 4 The contents of LLTO, PAN and graphene/CNTs were 40%, 54.2%, 5% and 0.8%, respectively.
The lithium battery is prepared by respectively adopting the lithium supplementing functional electrolyte film and the ceramic coating film for the solid-state lithium battery, which are obtained in the examples 1-5, and the specific steps are as follows:
step 1, preparing a positive plate, namely mixing nickel cobalt lithium manganate, carbon black and a binder (PVDF) according to a mass ratio of 95:2:3 for pulping, uniformly coating the slurry on a carbon-coated aluminum foil current collector, drying in a blowing oven at 80 ℃, and then drying in vacuum at 80 ℃ for 8 hours to prepare the positive plate;
step 2, preparing a negative plate, namely uniformly coating slurry on a copper foil current collector by mixing SiOx/graphite (SiOx: graphite=3:7, x is more than 0 and less than or equal to 2), carbon black and a styrene-butadiene emulsion binder according to the mass ratio of 94:1.8:4.2 and water as a solvent, drying in a blast oven at 55 ℃, and then vacuum drying at 60 ℃ for 12 hours to prepare the negative plate;
step 3, respectively adopting the lithium supplementing functional electrolyte membrane for the solid-state lithium battery and the comparative ceramic coating film prepared in the embodiments 1-5 for positive and negative electrodes according to n/p=1.05, manufacturing a 5Ah soft-package battery core by lamination, and welding, side sealing and top sealing the electrode lugs by one side of a framework layer;
and 4, adding an interface wetting agent (1M LiPF6 is dissolved in an organic solvent with the volume ratio of EC: DEC: DMC=1:1:1) into a glove box under the protection of argon, and sealing.
And 5, forming, sealing for two times and separating the volume to prepare the lithium battery.
And carrying out thermal shrinkage and thermal puncture tests on the prepared electrolyte membrane with the lithium supplementing function for the solid-state lithium battery and the common ceramic coating membrane.
Thermal shrinkage Property test referring to Standard ISO 14616-1997 test for Heat shrink films of polyethylene, ethylene copolymer and mixtures thereof-test for shrinkage stress, the samples were cut into square samples of 120mm by 120mm using an image measuring apparatus, 10cm lines were drawn on the samples in MD and TD directions, and heat shrinkage rates in MD and TD directions of films heat-treated at 180℃for 60 minutes were measured.
And (3) testing the thermal puncture performance, wherein a steel needle heated to 300 ℃ passes through the membrane surface at a speed of 100mm/min on a tensile machine, and measuring the pore diameter of the membrane surface by using an image measuring instrument.
TABLE 1,
300 ℃ thermal puncture test, membrane surface pore diameter (mm)
Example 1 2.69
Comparative example 1 (PE ceramic coating film) 4.99
Comparative example 2 (PP ceramic coating film) 5.284
As is clear from the comparison of fig. 3 and 4, which show that the electrolyte membrane in example 1 has significantly better temperature resistance than the conventional ceramic coating film, particularly PE ceramic coating film, after baking at 180 c, the film is completely broken and not formed.
According to the thermal puncture performance test, after the lithium-supplementing functional electrolyte membrane is subjected to thermal puncture at 300 ℃, the pore diameter of the membrane surface is obviously smaller than that of a comparative example, and the needling performance of the battery can be further improved.
Cycle stability test, cycle life curves in 1C (1c=5a) charge and discharge modes are shown in fig. 2, and it can be seen from the cycle performance of example 1 and comparative example batteries that the lithium ion battery can realize more stable cycle through the surplus lithium ions provided by the first cycle of the lithium supplementing compound in the lithium supplementing electrolyte film, and the example 1 can still have 100% capacity retention rate after 360 cycles of 1C cycle; in the comparative example, the cycle performance was deteriorated due to the low utilization efficiency of lithium ions, and the retention rate was 77.41% after 243 cycles.
Compared with the prior art, the lithium-supplementing functional electrolyte membrane for the solid-state lithium battery replaces the traditional lithium ion battery diaphragm, can supplement lithium ions for the first circle after the battery is assembled, improves the cycle performance of the battery, and does not damage the performance of the battery after the first circle is charged. The lithium supplementing electrolyte layer is filled in the framework layer and between the enhancement layers, so that good lithium supplementing can be realized, and the lithium supplementing agent can be prevented from falling into the electrolyte, so that the lithium supplementing efficiency is reduced. Meanwhile, the lithium supplementing electrolyte layer has controllable thickness, and the lithium supplementing amount can be easily adjusted according to a positive and negative electrode system. The inorganic solid electrolyte particles in the lithium supplementing electrolyte layer can not only increase lithium ion conduction, but also enhance the heat resistance of the diaphragm and reduce the thermal shrinkage and thermal puncture of the diaphragm.
While the preferred embodiments of the present invention have been described in detail, it should be clearly understood that the present invention may be variously modified and changed by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A preparation method of a lithium supplementing functional electrolyte membrane for a solid lithium battery is characterized by comprising the following steps: the method comprises the following specific steps:
s1, respectively weighing a lithium-containing compound, inorganic solid electrolyte particles, a binder and a conductive agent, respectively dispersing the weighed lithium-containing compound and inorganic solid electrolyte particles in NMP, and respectively ball-milling to prepare a lithium-containing compound dispersion liquid and an inorganic solid electrolyte particle dispersion liquid; simultaneously stirring and dissolving the weighed binder in NMP to prepare a binder solution;
s2, mixing the lithium-containing compound dispersion liquid and the inorganic solid electrolyte particle dispersion liquid according to the mass ratio, adding a conductive agent into the mixture, and continuing ball milling, dispersing and mixing to prepare a mixed dispersion liquid;
s3, adding the binder solution obtained in the step S1 into the mixed dispersion liquid obtained in the step S2, and performing ball milling and mixing to obtain uniform slurry;
s4, coating the uniform slurry obtained in the step S3 on the surface of one side, opposite to the reinforcing layer and the framework layer, of the reinforcing layer through a double unreeling mode, drying in an oven of a coating machine, and further forming a lithium supplementing electrolyte layer between the reinforcing layer and the framework layer, so that a lithium supplementing functional electrolyte membrane for a solid-state lithium battery is obtained;
the skeleton layer is a three-dimensional porous structure nonwoven film and comprises a first polymer base material, wherein the first polymer base material is one of cellulose and PET, PI, PVDF, PA, PVC;
the reinforcing layer comprises a second polymer base material, wherein the second polymer base material is one of PE, PP and PE/PP/PE;
the lithium-supplementing electrolyte layer obtained in the step S4 contains 10% -45% of lithium-containing compound, the inorganic solid electrolyte particles 50% -80%, the binder 3.5% -10% and the conductive agent 0.5% -2%.
2. The method for producing a lithium-compensating functional electrolyte membrane for a solid-state lithium battery according to claim 1, characterized in that: in the step S1, the binder was dissolved in NMP with stirring at a solid content of 10% to prepare a binder solution.
3. The method for producing a lithium-compensating functional electrolyte membrane for a solid-state lithium battery according to claim 1, characterized in that: after ball milling in the step S1, the particle size of the lithium-containing compound is 0.1-2 mu m.
4. The method for producing a lithium-compensating functional electrolyte membrane for a solid-state lithium battery according to claim 1, characterized in that: after ball milling in the step S1, the particle size of the inorganic solid electrolyte particles is 0.1-2 mu m.
5. The method for producing a lithium-compensating functional electrolyte membrane for a solid state lithium battery according to any one of claims 1 to 4, characterized in that: the lithium-containing compound in the step S1 includes at least one of lithium iron oxide, lithium nickel oxide, lithium cobalt oxide, organic lithium salt, lithium oxide, lithium sulfide, lithium phosphide, and lithium nitride.
6. The method for producing a lithium-compensating functional electrolyte membrane for a solid state lithium battery according to claim 5, characterized in that: the lithium-containing compound in the step S1 is Li 5 FeO 4 、Li 5 Fe 5 O 8 、Li 6 CoO 4 、Li 2 NiO 2 、Li 2 O、Li 2 S、Li 3 P、Li 3 N、Li 2 O 2 、Li 2 C 2 O 4 、Li 2 At least one of DHBN.
7. The method for producing a lithium-compensating functional electrolyte membrane for a solid state lithium battery according to any one of claims 1 to 4, characterized in that:
the inorganic solid electrolyte particles in the step S1 are of a NASICON structureIs of the formula LiM 2 (PO 4 ) 3 、Li 1+x Al x Ti 2-x (PO 4 ) 3 And Li (lithium) 1+x Al x Ge 2-x (PO 4 ) 3 Wherein M is one of Ti, ge and Hf, and x is more than 0 and less than 2;
or the inorganic solid electrolyte particles are of perovskite structure, and the chemical formula of the inorganic solid electrolyte particles is Li 0.34 La 0.56 TiO 3 And/or Li 0.5 La 0.5 TiO 3 ；
Or the inorganic solid electrolyte particles are LISICON structures, and the chemical formula of the inorganic solid electrolyte particles is Li 14 Zn(GeO 4 ) 4 ；
Or the inorganic solid electrolyte particles are garnet-type structures, and the chemical formula of the inorganic solid electrolyte particles is Li 5 La 3 R 2 O 12 、Li 6 ALa 2 R 2 O 12 、Li 5.5 La 3 R 1.75 D 0.25 O 12 、Li 7 La 3 Zr 2 O 12 And Li (lithium) 7.06 E 3 Y 0.06 Zr 1.94 O 12 Wherein R is Nb or Ta, A is one of Ca, sr and Ba, D is In or Zr, and E is one of La, nb and Ta;
or the inorganic solid electrolyte particles are of an inverse perovskite structure, and the chemical formula of the inorganic solid electrolyte particles is Li 3 OX, wherein X is one of F, cl and Br;
or the inorganic solid electrolyte particles are in a glass state, and the inorganic solid electrolyte particles are sulfide Li 10 GeP 2 S 12 、Li 2 S-SiS 2 、Li 2 S-P 2 S 5 、70Li 2 S-30P 2 S 5 One or more of the following.
8. The method for producing a lithium-compensating functional electrolyte membrane for a solid state lithium battery according to any one of claims 1 to 4, characterized in that: the binder in the step S1 is at least one of PVDF and PVDF-HFP, PVP, PEO, PAN, EVA, PMMA;
the conductive agent in the step S2 is one or more of Super-P, ketjen black, CNTs and graphene.
9. The method for producing a lithium-compensating functional electrolyte membrane for a solid-state lithium battery according to claim 1, characterized in that: the temperature of the oven in the step S4 is 60-80 ℃.
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