CN105885048A - Polythioquinone and preparation method thereof - Google Patents

Abstract

The invention relates to a novel polythioquinone and a preparation method thereof. The preparation method comprises the following steps: dissolving tetrachloroquinone in an organic solvent which is intersoluble with water, dissolving sodium sulfide or sodium polysulfide in water, dropwisely adding the sodium sulfide or sodium polysulfide water solution into the tetrachloroquinone-containing solution, carrying out polymerization reaction completely, and treating to obtain the polythioquinone powder. The polythioquinone has the advantages of higher polymerization degree and higher yield (up to 80% or above). The preparation method is simple and easy to implement, and has favorable yield and universality. The obtained polymer powder can be used as an electrode material for secondary batteries, supercapacitors and other energy storage devices.

Description

A kind of polysulfide is for benzoquinones and preparation method thereof

Technical field

The present invention relates to a kind of polysulfide for benzoquinones and preparation method thereof.This polymer can be used for organolithium cell positive material, it is possible to Negative material etc. for aquo-lithium ion battery.

Background technology

Compared with inorganic material, organic electrodes material has theoretical specific capacity high, cheap (being not related to expensive element), capable of circulation The advantages such as utilization and height can design, and need not high temperature sintering conventional in the preparation of inorganic lithium ion intercalation materials, carbon discharge capacity is low. The most in recent years, some organic electrode materials can realize green syt completely and directly extract from plant, the most organic Thing electrode material is the ergastic substances that a class has wide application prospect, and existing a large amount of relevant quinones electrodes are at organolithium two The report applied in primary cell field and patent application.Tang causes far to wait (CN1564348A) to synthesize poly-1-aminoanthraquinone and poly-1,5- Diamino-anthraquinone, anthraquinone radicals generation redox reaction in charge and discharge process, layer/polyaniline conductive skeleton generation p-doping/take off and mix Miscellaneous process.Owing to the introducing of electrically conductive polyaniline improves the electric conductivity of electrode, in electrode fabrication, conductive agent addition is greatly decreased. Song etc. use 1, and 5-dichloroanthraquinone and vulcanized sodium react and obtained anthraquinonyl sulfide polymer, are vulcanized by carbonyl-containing organics Polymerization, improves cyclical stability and the electric conductivity of material.But this preparation method need organic solvent in anhydrous conditions is carried out. The quantity continuing to increase quinonyl in the molecular structure can increase capacity theoretically, and therefore researcher is to many quinones or Polyphenols chemical combination Thing expands research.Wang Anbang etc. (CN102311534A) are prepared for Isosorbide-5-Nitrae, 5,8-tetrahydroxy-9, dimer tetrahydrochysene six quinone of 10-anthraquinone, It is prepared for many quinones in a simple way, is effectively increased capacity, reduce dissolubility.Wang Yuanyuan etc. (CN103803531A) oxidant is joined 1, in the mixed sols of 5-diamino-anthraquinone and graphite oxide, prepares poly-1,5-diamino Base anthraquinone and the composite of Graphene, have preferable electric conductivity and stability.

The theoretical capacity of organic quinones is high, and average working voltage is typically at 2.0～2.5V (vs.Li/Li⁺), the highest it is less than 2.8V(vs.Li/Li⁺), and there is molecule designability；Compared with common inorganic material, organic quinones room for promotion is very Greatly, it is the preferable class high-capacity lithium ion cell electrode material of application prospect.But organic compound is typically insulator, electronics Difficulty is transmitted mutually at body；And be prone to dissolve under the effect of water polar solvent, cause organic material high rate performance and stable circulation Property is poor.Accordingly, it would be desirable on molecular level designs, by polymerization, the approach such as In-situ reaction of conductive material, develop height Capacity and the electrode material that can be used for secondary energy storage battery of high cyclical stability.In the substituent of quinone derivatives, chloro is Electron-withdrawing group is again hydrophobic group, and the solubility that chloro replaces benzoquinones is relatively low, and electrode potential is higher.1972, Alt etc. Have studied emphatically chloranil chemical property in aqueous and single electrode charge-discharge characteristic.Under strongly acidic conditions, chloranil Electrode reaction be a simple step two electron redox course of reaction, single electrode charging and discharging curve only one of which platform and circulation 50 times without significantly decay.To this end, carry out sulphur generation polymerization with tetrachloroquinone for monomer, structure can be prepared more through single step reaction For stable quinones polymeric material.

Summary of the invention

It is an object of the invention to prepare high stability quinones polymer with a kind of simple method, can be as organolithium battery Positive electrode is it can also be used to the negative material of aquo-lithium ion battery.

It is as follows for benzoquinones method step that the present invention prepares polysulfide: is dissolved in by tetrachloroquinone in organic solvent miscible with water, then, By soluble in water to vulcanized sodium or sodium polysulfide, then vulcanized sodium or aqueous sodium polysulfide are instilled in the solution containing tetrachloroquinone, Reaction temperature is 0～300 DEG C, and the reaction time is 10～72h, makes reactive polymeric complete；Filter, wash, dry, First clean 2～3 times with organic solvent for the washing of benzoquinones powder to polysulfide, finally clean by deionized water, obtain polysulfide for benzoquinones；

Organic solvent is acetonitrile, 1-METHYLPYRROLIDONE, DMF or ethyl acetate；

The mol ratio of vulcanized sodium or sodium polysulfide and monomer tetrachloroquinone is 4～20: 1.

Beneficial effects of the present invention: this preparation method economical and effective, have good yield and universality, is suitable for batch and prepares. Obtained polysulfide is high for the benzoquinones degree of polymerization, has high stability in polar solvent, and yield can reach more than 80%.Gained Polymer powder can be as the electrode material of the energy storage device such as secondary cell, ultracapacitor.

Accompanying drawing explanation

Fig. 1 polysulfide for benzoquinones electrode at 5M LiNO₃Typical charging and discharging curve in the aqueous solution

Ordinate is electrode potential (V vs.SCE), and abscissa is discharge and recharge time (min).

Fig. 2 polysulfide for benzoquinones electrode at 5M LiNO₃In the aqueous solution, specific discharge capacity is with the change of cycle-index

Ordinate is specific discharge capacity (mAh g^-1), abscissa is cycle-index.

Detailed description of the invention

Example 1

Tetrachloroquinone (5g, 0.02mol) is dissolved in DMF, by Na₂S·9H₂O (19.2g, 0.08mol) Soluble in water aqueous sodium polysulfide is made with sulphur heating.Aqueous sodium polysulfide is instilled the N, N-bis-containing tetrachloroquinone In NMF solution, at 240 DEG C, heating is stirred at reflux 48 hours and makes its reactive polymeric complete, filters, uses deionization respectively Water and acetone clean for several times, i.e. obtain brownish black product, and drying is weighed, yield 82%.

Example 2

Tetrachloroquinone (5g, 0.02mol) is dissolved in 1-METHYLPYRROLIDONE, by Na₂S·9H₂O (19.2g, 0.08mol) is dissolved in In water.Being instilled by sodium sulfide solution in the N-crassitude solution containing tetrachloroquinone, at 180 DEG C, heating is stirred at reflux 52 Hour make its reactive polymeric complete, filter, clean for several times with deionized water and acetone respectively, i.e. obtain gel brownish black product, Drying is weighed, yield 85%.

Example 3

Tetrachloroquinone (5g, 0.02mol) is dissolved in ethyl acetate, by Na₂S·9H₂O (19.2g, 0.08mol) and sulphur are dissolved in Water is made aqueous sodium polysulfide.Water-soluble for sodium polysulfide instillation is contained in the ethyl acetate solution of tetrachloroquinone, at 150 DEG C Heating is stirred at reflux 68 hours and makes its reactive polymeric complete, filters, and cleans for several times with deionized water and acetone respectively, is i.e. coagulated Gluey brownish black product, drying weighs, yield 86%.

Example 4

Tetrachloroquinone (5g, 0.02mol) is dissolved in DMF, is subsequently adding 0.5g acetylene black, ultrasonic Dispersion makes it mix.By Na₂S·9H₂O (19.2g, 0.08mol) and sulphur is soluble in water makes aqueous sodium polysulfide.Will The water-soluble instillation of sodium polysulfide contains in the DMF solution of tetrachloroquinone and acetylene black, adds thermal agitation at 180 DEG C Reflux and within 72 hours, make its reactive polymeric complete, filter, clean for several times with deionized water and acetone respectively, i.e. obtain gel dark brown Look combination product, drying weighs, and yield reaches 83%.

Polysulfide produced above is high for the benzoquinones degree of polymerization, has high stability in polar solvent, and yield can reach more than 80%. The polymer powder of gained can be as the electrode material of the energy storage device such as secondary cell, ultracapacitor.

Claims (1)

1. a polysulfide is for benzoquinones and preparation method thereof, it is characterised in that polysulfide is as follows for quinone hardening Preparation Method step:

Tetrachloroquinone is dissolved in organic solvent miscible with water, then, by soluble in water to vulcanized sodium or sodium polysulfide, then will Vulcanized sodium or aqueous sodium polysulfide instill in the solution containing tetrachloroquinone, and reaction temperature is 0～300 DEG C, and the reaction time is 10～72h, make reactive polymeric complete；Filter, wash, dry, obtain polysulfide and wash first with organic molten for benzoquinones powder Agent is cleaned 2～3 times, finally cleans by deionized water, obtains polysulfide for benzoquinones；

Organic solvent is acetonitrile, 1-METHYLPYRROLIDONE, DMF or ethyl acetate；

The mol ratio of vulcanized sodium or sodium polysulfide and monomer tetrachloroquinone is 4～20: 1.