CN102005611A - Polymer electrolyte and preparation method and application thereof - Google Patents
Polymer electrolyte and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses polymer electrolyte and a preparation method and application thereof. The provided polymer electrolyte consists of a high polymer matrix, lithium salt, an organic small molecular plasticizer and/or inorganic superfine nanoparticles. The provided polymer electrolyte has high ionic conductivity, high toughness and high-temperature resistance, and when the polymer electrolyte is used as lithium ion secondary battery electrolyte, the structure of a commercial lithium ion secondary battery is simplified, the structure of the lithium ion secondary battery is enriched, and simultaneously the potential safety hazard in the traditional lithium ion secondary battery can be effectively avoided. Meanwhile, in the process of preparing a lithium battery from the provided polymer electrolyte, the conventional commercial micron-sized graphite anode can be replaced by a metal lithium foil, so the prepared novel lithium ion battery has higher energy density and power density.
Description
Technical field
The present invention relates to a kind of polymer dielectric and preparation method thereof and application.
Background technology
Because plurality of advantages such as have that operating voltage height, energy density are big, good cycle, self discharge are little, the energy that lithium rechargeable battery has been widely applied to technical fields such as notebook computer, mobile phone, UPS stores and the conversion aspect, also has broad application prospects in industries such as electric automobile and car batteries.Yet from the structure of present widely used lithium rechargeable battery, still there is the shortcoming of following two aspects in it: the electrolyte that use (1) as liquid electrolyte (for example: LiPF
6-EC-DMC-DEC, LiPF
6Liquid electrolytes such as-EC-DEC), it is inflammable, volatile and leak from battery easily, makes the liquid electrolyte base lithium ion secondary battery have tangible potential safety hazard; (2) negative pole of Shi Yonging is micron-sized ball-type fossil China ink, its theoretical capacity (372mA h g
-1) still lower, make the raising aspect of lithium rechargeable battery energy density have theoretic bottleneck.Therefore, selecting to have the negative material of height ratio capacity more is one of the method that further improves the energy density of lithium rechargeable battery.In can be used for all negative materials of lithium rechargeable battery, lithium metal has the highest theoretical capacity (3862mA h g
-1), still, in charging and discharging process,, can penetrate porous barrier film and the short circuit of inside battery takes place at a large amount of lithium Zhi Jing that its surface produces, there is serious safety issue, make it can not directly replace graphite cathode in the present commercial li-ion battery.(3) the porousness barrier film of Shi Yonging is very easily because the generation of Zhi Jing, the introducing of impurity particle etc. are former thereby penetrated, thereby the short circuit phenomenon of inside battery takes place.Therefore, select and the content regulation and control by structural design, composition, preparation has the polymer dielectric than high ion-conductivity, has very important significance for the lithium rechargeable battery of developing high-energy-density, high security.
Summary of the invention
The purpose of this invention is to provide a kind of polymer dielectric and preparation method thereof and application.
Polymer dielectric provided by the invention comprises high molecular polymer, lithium salts and additive; Described additive is selected from least a in organic molecule plasticizer and the inorganic nanoparticles.
In the above-mentioned polymer dielectric, lithium salts and organic molecule plasticizer are dissolved among the high molecular polymer matrix, and inorganic nanoparticles is scattered among the polymer substrate equably.This polymer dielectric also can only be made up of said components.
Described high molecular polymer is selected from least a in polymethyl methacrylate (PMMA), Kynoar (PVdF), polytetrafluoroethylene (PTFE), poly(ethylene oxide) (PEO), polyethylene-polypropylene-polyethylene block copolymer, polyvinyl alcohol (PVA) and the polyvinyl butyral resin (PVB), at least a in preferably polytetrafluoroethylene (PTFE) and the poly(ethylene oxide) (PEO); The weight average molecular weight of described high molecular polymer is 5 * 10
4-5 * 10
6, specifically can be 9 * 10
4-8 * 10
5, 9 * 10
4-2 * 10
6, 9 * 10
4-7 * 10
5, 7 * 10
5-2 * 10
6Or 8 * 10
5-2 * 10
6, preferred 1 * 10
5-1 * 10
6
Described lithium salts closes lithium borate (LiBOB) for two oxalic acid;
Described organic molecule plasticizer is selected from least a in propene carbonate (PC), ethylene carbonate (EC), succinonitrile (SN) and the polyethylene glycol (PEG), preferred succinonitrile (SN); The degree of polymerization of described polyethylene glycol is 2-400, preferred 10-100, more preferably 20;
Described inorganic nanoparticles is selected from least a in titanium dioxide nanoparticle, nano alumina particles, nano oxidized magnesium granules, nano oxidized silicon grain, nano zircite particle and the nano granular of zinc oxide, preferred nano oxidized silicon grain; The particle diameter of described inorganic nanoparticles is the 1-500 nanometer, specifically can be 5-50 nanometer, 10-50 nanometer, 10-100 nanometer or 50-100 nanometer, preferred 5-100 nanometer;
The construction unit in the described high molecular polymer and the mol ratio of described lithium salts are 5～30: 1, specifically can be 10-23.5: 1,10-20: 1,15-23.5: 1,10-20: 1 or 15-18: 1, preferred 15～20: 1, the mol ratio of described organic molecule plasticizer and described lithium salts is 0.2～5: 1, specifically can be 1.8-3.7: 1,1.96-3.7: 1,2-3.7: 1,2-3.3: 1 or 3.3-3.7: 1, preferred 1～2: 1; The mass ratio of described inorganic nanoparticles and described lithium salts is 1: 0.9～20, specifically can be 1: 0.9-2.1,1: 1.9-3,1: 1.8-1.9 or 1: 1.8-2.1, preferred 1: 5～10.
The method of the above-mentioned polymer dielectric of preparation provided by the invention, comprise the steps: described lithium salts and described additive in solvent behind the mixing, obtain mixed liquor after adding described high molecular polymer mixing again, described mixed liquor is shifted surface in smooth substrate, obtain described polymer dielectric after the drying.
In this method, described solvent is selected from water, ethanol, methyl alcohol, acetonitrile, N, at least a in dinethylformamide, N-methyl pyrrolidone, acetate, ether, acetone, dimethyl sulfoxide (DMSO), ethyl acetate, benzinum and the oxolane, preferred acetonitrile.
The mass ratio of described solvent and described lithium salts is 20～200: 1, specifically can be 67-100: 1,67-83: 1,67-90: 1,83-100: 1 or 90-100: 1, and preferred 50-100: 1; The viscosity of described Polymer Solution is 1～20Pas, specifically can be 3.6-13.5Pas, 5.2-13.5Pas, 5.2-12.2Pas, 9.5-13.5Pas or 9.7-12.2Pas, preferred 5-10Pas.
In these method two mixing steps, the method for mixing be selected from conventional stirring and ultrasonic at least a; The described adding again in the described high molecular polymer mixing step, mixing time is 3-30 hour, preferred 8-15 hour;
The material that constitutes described smooth substrate is polytetrafluoroethylene, glass or polypropylene;
In the described transfer step, various transfer methods commonly used all are suitable for, as can be casting, spin-coating method or cladding process, preferred cladding process;
In the described drying steps, atmosphere is selected from least a in vacuum, air, oxygen, nitrogen, argon gas, hydrogen, carbon dioxide and the helium, in the described vacuum atmosphere, vacuum degree is-70KPa～-100KPa, preferably-85KPa～-95KPa, more preferably-90KPa, temperature is-50～100 ℃, specifically can be 30-80 ℃, 50-60 ℃ or 30-50 ℃, preferred 0～60 ℃, time is 1～48 hour, specifically can be 10-20 hour, 15-24 hour, 13-24 hour or 13-20 hour, preferred 6～20 hours.
In addition, the application of polymer dielectric provided by the invention in the preparation lithium ion battery also belongs to protection scope of the present invention.
Polymer dielectric provided by the invention has high ionic conductivity, high toughness and resistance to elevated temperatures, during used as the lithium rechargeable battery electrolyte, can replace barrier film and liquid electrolyte in the present commercial li-ion battery simultaneously, simplified the structure of commercial li-ion secondary cell, enrich the structure of lithium rechargeable battery, can avoid simultaneously the potential safety hazard of the contingent leakage of traditional lithium rechargeable battery, aspect such as inflammable and explosive effectively.Simultaneously, during with the lithium battery of polymer dielectric provided by the invention preparation, can replace commercial at present micron order graphite cathode, make the new type lithium ion battery of preparing have higher energy density and power density with metallic lithium foil.Therefore, use polymer dielectric provided by the invention, can develop the lithium battery that has high security, high plasticity, high-energy-density and high power density concurrently, the development of lithium ion battery industry is had very important significance.
Description of drawings
Fig. 1 is the optical photograph of No. 2 polymer dielectric films among the embodiment 2.
Fig. 2 is scanning electron microscopy (SEM) photo on No. 2 polymer dielectric film surfaces among the embodiment 2.
Fig. 3 is the stability data curve of the ionic conductivity of No. 2 polymer dielectric films under 60 ℃ among the embodiment 2.
Fig. 4 is the optical photograph of No. 6 polymer dielectric films among the embodiment 6.
Fig. 5 is the SEM photo in No. 6 polymer dielectric film cross sections among the embodiment 6.
Fig. 6 is the curve of X-ray diffraction (XRD) test data of No. 6 polymer dielectric films among the embodiment 6.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.Method is conventional method if no special instructions described in the following embodiment, and used reaction raw materials is from open commercial sources purchase and obtains.
Embodiment 1, No. 1 polymer dielectric of preparation
Under ultrasonic condition, with 1.5g LiBOB, 1.24g SN (mol ratio of SN and LiBOB is 2: 1) and 0.8g nano magnesia (particle diameter is 10 nanometers) join in the 150g ethanol successively, obtain uniform white suspension-turbid liquid; Then, adding the 8g molecular weight in suspension-turbid liquid is 8 * 10
5PVA (construction unit is a vinyl alcohol, and the mol ratio of this construction unit and lithium salts is 23.5: 1), ultrasonic agitation is after 8 hours, obtains the outstanding turbid polymer suspension (viscosity is 9.5Pas) of uniform nano magnesia; Then, with spin-coating method the polymer suspension that obtains is coated on smooth glass surface equably; At last, the glass 50 ℃ of dryings in nitrogen atmosphere that this applied polymer suspension obtain polymer dielectric film No. 1 after 10 hours.
Under stirring condition, 2g LiBOB and 3g PC (mol ratio of PC and LiBOB is 3.3: 1) are joined in the 200gN-methyl pyrrolidone successively, obtain the solution of homogeneous transparent; Then, adding the 12g molecular weight in clear solution is 1 * 10
5PVdF (construction unit is a vinylidene fluoride, and the mol ratio of this construction unit and lithium salts is 18: 1), stir after 8 hours, obtain uniform milky Polymer Solution (viscosity is 5.2Pas); Then, with the scraper cladding process Polymer Solution that obtains is coated on smooth glass surface; At last, the glass that this has been applied Polymer Solution vacuum degree for the vacuum degree condition of-90KPa under 80 ℃ of dryings obtain polymer dielectric after 15 hours No. 2.
Embodiment 3, No. 3 polymer dielectrics of preparation
Under the condition of ultrasonic agitation, 1.8g LiBOB and 2g nano aluminium oxide (particle diameter is 100 nanometers) are joined 120g successively by acetone, N, in the mixed solution that dinethylformamide and benzinum (volume ratio is 1: 1: 2) are formed, obtain uniform suspension-turbid liquid; Then, adding the 14g molecular weight in this suspension-turbid liquid is 1 * 10
6PMMA (construction unit is a methyl methacrylate, and the mol ratio of this construction unit and lithium salts is 15: 1), stir after 15 hours, obtain uniform milky polymer suspension (viscosity is 12.2Pas); Then, with the scraper cladding process Polymer Solution that obtains is coated on smooth ptfe surface; At last, the polyfluortetraethylene plate 60 ℃ of dryings in carbon dioxide atmosphere that this applied polymer suspension obtain polymer dielectric No. 3 after 13 hours.
Embodiment 4, No. 4 polymer dielectrics of preparation
Under the condition of ultrasonic agitation, with 1.8g LiBOB, 1.5g PEG (degree of polymerization is 20) (mol ratio of PEG and LiBOB is 3.7: 1) and 0.86g nano silicon oxide (particle diameter is 50 nanometers) join in the mixed solution that 150g is made up of water and ethanol (volume ratio is 1: 1) successively, obtain uniform suspension-turbid liquid; Then, adding the 13g molecular weight in this suspension-turbid liquid is 2 * 10
6PVB (construction unit is a vinyl butyral, and the mol ratio of this construction unit and lithium salts is 10: 1), stir after 8 hours, obtain uniform milky polymer suspension (viscosity is 13.5Pas); Then, with direct casting the Polymer Solution that obtains is coated on the smooth polypropylene surface; At last, this has been applied the polypropylene board of polymer suspension 50 ℃ of dryings in mist (volume ratio is 90: the 10) atmosphere of nitrogen and hydrogen and obtained polymer dielectric after 10 hours No. 4.
Embodiment 5, No. 5 polymer dielectrics of preparation
Under ultrasonic condition, with 2g LiBOB, 1.5g EC (mol ratio of EC and LiBOB is 1.96: 1) and 1.1g nano zine oxide (particle diameter is 5 nanometers) join in the mixed solution that 200g is made up of dimethyl sulfoxide (DMSO) and water (volume ratio is 2: 1) successively, obtain uniform suspension-turbid liquid; Then, adding the 20.6g molecular weight in this suspension-turbid liquid is 9 * 10
4PTFE (construction unit is a tetrafluoroethene, and the mol ratio of this construction unit and lithium salts is 20: 1), stir after 20 hours, obtain uniform milky polymer suspension (viscosity is 3.6Pas); Then, the Polymer Solution that obtains is coated on the smooth glass pane surface with the scraper cladding process: last, these glass plate 80 ℃ of dryings in helium atmosphere that applied polymer suspension are obtained polymer dielectric No. 5 after 20 hours.
Embodiment 6, No. 6 polymer dielectrics of preparation
Under stirring condition, 2g LiBOB and 1.5g SN (mol ratio of SN and LiBOB is 1.8: 1) are joined in the 180g acetonitrile, obtain uniform solution; Then, adding the 7.3g molecular weight in this solution is 7 * 10
5PEO (construction unit is an oxirane, and the mol ratio of this construction unit and lithium salts is 16: 1), stir after 16 hours, obtain milky Polymer Solution (viscosity is 9.7Pas); Then, with the scraper cladding process Polymer Solution that obtains is coated on the smooth polyfluortetraethylene plate surface; At last, the polyfluortetraethylene plate 30 ℃ of dryings in air atmosphere that this applied polymer suspension obtain polymer dielectric No. 6 after 24 hours.
The sign of polymer dielectric film and result thereof:
Utilize ionic conductance that AC impedance spectrometry (Parstat 2273 senior electrochemical workstations) tested 1～No. 6 polymer dielectric with variation of temperature situation and the stability of conductivity (seeing Table 1) at a certain temperature; Shone the electrolytical optical photograph of resulting polymers with digital camera; With powder x-ray diffraction (Rigaku DmaxrB, CuK
αRay) tested the crystalline structure of polymer dielectric; Surface, cross section pattern and the performance of polymer dielectric have been observed with scanning electron microscopy (JEOL-6700F); With rotary digital viscosimeter (NDJ-8S) viscosity of gained mixed liquor (Polymer Solution or suspension-turbid liquid) is measured.
The gained result is as shown in table 1.
The conductivity data of table 1, polymer dielectric
As shown in Table 1, the electrolytical ionic conductivity of resulting polymers raises along with the rising of temperature, and under higher temperature (＞50 ℃), the electrolytical ionic conductivity of resulting polymers can satisfy lithium ion battery to the conductive requirement of electrolyte ion; Shown in the SEM photo of the optical photograph of Fig. 1 and Fig. 4 and Fig. 2 and Fig. 5, the polymer dielectric that makes is the complete film structure of good self-supporting, can directly replace liquid electrolyte and barrier film in the current lithium ion simultaneously; As shown in Figure 3, the resulting polymers electrolyte has good ionic conduction stability under higher temperature; As shown in Figure 6, lithium salts in the adding polymer dielectric and organic molecule additive are among the molecule rank is scattered in polymer substrate equably.
Assembling poly-lithium battery and battery performance test:
With the lithium paper tinsel is negative pole, LiFePO
4For the electrode slice of active material is anodal, No. 6 polymer dielectrics are electrolyte, assemble poly-lithium battery in the argon gas glove box, and have tested the charge-discharge performance (seeing Table 2) of the poly-lithium battery that is assembled on the LAND cell tester.
The 0.1C specific discharge capacity data of the polymer battery of table 2, assembling
As shown in table 2, polymer dielectric provided by the invention can show higher discharge capacity with this lithium battery that assembles as the electrolyte and the barrier film of lithium ion battery fully under higher temperature.
Claims (10)
1. a polymer dielectric comprises high molecular polymer, lithium salts and additive; Described additive is selected from least a in organic molecule plasticizer and the inorganic nanoparticles.
2. polymer dielectric according to claim 1, it is characterized in that: described high molecular polymer is selected from least a in polymethyl methacrylate, Kynoar, polytetrafluoroethylene, poly(ethylene oxide), polyethylene-polypropylene-polyethylene block copolymer, polyvinyl alcohol and the polyvinyl butyral resin, at least a in preferably polytetrafluoroethylene and the poly(ethylene oxide);
Described lithium salts closes lithium borate for two oxalic acid;
Described organic molecule plasticizer is selected from least a in propene carbonate, ethylene carbonate, succinonitrile and the polyethylene glycol, preferred succinonitrile; The degree of polymerization of described polyethylene glycol is 2～400, preferred 10～100;
Described inorganic nanoparticles is selected from least a in titanium dioxide nanoparticle, nano alumina particles, nano oxidized magnesium granules, nano oxidized silicon grain, nano zircite particle and the nano granular of zinc oxide, preferred nano oxidized silicon grain.
3. polymer dielectric according to claim 1 and 2 is characterized in that: the weight average molecular weight of described high molecular polymer is 5 * 10
4～5 * 10
6, preferred 1 * 10
5～1 * 10
6
The particle diameter of described inorganic nanoparticles is 1～500 nanometer, preferred 5～100 nanometers;
The construction unit in the described high molecular polymer and the mol ratio of described lithium salts are 5～30: 1, preferred 15～20: 1, the mol ratio of described organic molecule plasticizer and described lithium salts is 0.2～5: 1, preferred 1～2: 1, the mass ratio of described inorganic nanoparticles and described lithium salts is 1: 0.9～20, preferred 1: 5～10.
4. according to the arbitrary described polymer dielectric of claim 1-3, it is characterized in that: described polymer dielectric is made up of described high molecular polymer, described lithium salts and described additive.
5. according to the arbitrary described polymer dielectric of claim 1-4, it is characterized in that: described polymer dielectric is to get according to the arbitrary described method preparation of claim 6-9.
6. method for preparing the arbitrary described polymer dielectric of claim 1-5, comprise the steps: described lithium salts and described additive in solvent behind the mixing, obtain mixed liquor after adding described high molecular polymer mixing again, described mixed liquor is shifted surface in smooth substrate, obtain described polymer dielectric after the drying.
7. method according to claim 6, it is characterized in that: described solvent is selected from water, ethanol, methyl alcohol, acetonitrile, N, at least a in dinethylformamide, N-methyl pyrrolidone, acetate, ether, acetone, dimethyl sulfoxide (DMSO), ethyl acetate, benzinum and the oxolane, preferred acetonitrile.
8. according to claim 6 or 7 described methods, it is characterized in that: the construction unit in the described high molecular polymer and the mol ratio of described lithium salts are 5～30: 1, preferred 15～20: 1, the mol ratio of described organic molecule plasticizer and described lithium salts is 0.2-5: 1, preferred 1～2: 1, the mass ratio of described inorganic nanoparticles and described lithium salts is 1: 0.9～20, preferred 1: 5～10; The mass ratio of described solvent and described lithium salts is 20～200: 1, preferred 50～100: 1;
The viscosity of described mixed liquor is 1～20Pas, preferred 5～10Pas.
9. according to the arbitrary described method of claim 6-8, it is characterized in that: the described adding again in the described high molecular polymer mixing step, mixing time is 3～30 hours, preferred 8～15 hours;
The material that constitutes described smooth substrate is polytetrafluoroethylene, glass or polypropylene;
In the described drying steps, atmosphere is selected from least a in vacuum, air, oxygen, nitrogen, argon gas, hydrogen, carbon dioxide and the helium, and in the described vacuum atmosphere, vacuum degree is-70KPa～-100KPa, preferred-85KPa～-95KPa; Temperature is-50～100 ℃, preferred 0～60 ℃; Time is 1～48 hour, preferred 6～20 hours.
10. the application of the arbitrary described polymer dielectric of claim 1-5 in the preparation lithium ion battery.
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