CN106654216A - Titanium zirconium phosphate-containing positive electrode material of lithium-sulfur battery and preparation method for positive electrode material - Google Patents

Titanium zirconium phosphate-containing positive electrode material of lithium-sulfur battery and preparation method for positive electrode material Download PDF

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CN106654216A
CN106654216A CN201710009597.XA CN201710009597A CN106654216A CN 106654216 A CN106654216 A CN 106654216A CN 201710009597 A CN201710009597 A CN 201710009597A CN 106654216 A CN106654216 A CN 106654216A
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titanium
sulphur
positive electrode
phosphate
phosphoric acid
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CN106654216B (en
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姜华
周海燕
杨辉
姜玮
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Anhui Tongneng New Energy Technology Co ltd
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HAITAI NANO MATERIAL CO Ltd NANJING
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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
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention discloses a titanium zirconium phosphate-containing positive electrode material of a lithium-sulfur battery and a preparation method for the positive electrode material. The positive electrode material comprises a conductive additive, sulfur and titanium zirconium phosphate at the mass ratio of (0.001-2) to 1 to (0.1-1); the sulfur is loaded to the interiors and the surfaces of the conductive additive and titanium zirconium phosphate; and the preparation method comprises the steps of dissolving a titanium salt and a zirconium salt into deionized water, adding a phosphorus-containing compound, regulating pH to 3-9 and reacting for 1-4h, standing for 10-20h, and then filtering, washing and drying to obtain titanium zirconium phosphate; and then adding the conductive agent, sulphur and titanium zirconium phosphate into a solvent to be grinded and dried, and next, performing calcining in an inert gas. The positive electrode material has the advantages of high conductivity, high cycling stability after 20 charging-discharging cycles, and relatively long service life and high energy density; and in addition, the positive electrode material is simple in preparation process, mild in synthesis condition, short in reaction time, and low in cost.

Description

A kind of sulphur anode material of lithium battery of phosphoric acid zirconium titanium and preparation method thereof
Technical field
The invention belongs to sulphur field of lithium, more particularly to a kind of sulphur anode material of lithium battery and its system of phosphoric acid zirconium titanium Preparation Method.
Background technology
The battery developed rapidly in the urgent need to developing higher energy density of electric vehicle and mobile electronic device.At present, Though the laboratory specific energy of lithium ion battery has reached 250Wh/kg, limited by positive electrode specific capacity, its specific energy is very It is difficult to improve a lot.Charging voltage is improved in order to further improve the specific capacity of lithium ion battery in prior art, but The appearance of aggravation safety problem in order to meet the demand to energy, has been developed new chemical energy storage by this in prior art System.
In new energy storage system, with lithium metal as negative pole, the theoretical specific energy of lithium-sulfur cell of the elemental sulfur as positive pole can 2600Wh/kg (theoretical specific capacity of lithium and sulphur is respectively 3860mAh/g and 1675mAh/g) is reached, much larger than being made at this stage Commercialization secondary cell.Additionally, elemental sulfur is cheap, eco-friendly characteristic makes the energy storage system great commercial value again. But in the prior art, not high to the utilization rate of positive active material sulphur in lithium-sulfur cell, its Capacity fading is serious, follows Ring poor-performing, and chemical property is not good.In order to improve the performance of lithium-sulfur cell, current people are devoted to lithium-sulfur cell The modified research of positive electrode, to improve its electric conductivity and cycle performance.For example sulphur is filled out in mesoporous carbon space, mesoporous carbon Addition improves electric conductivity；In addition with research worker sulphur is modified using conducting polymer, conducting polymer plus Entering can be effectively improved the cycle performance of lithium-sulfur cell.Although however, above-mentioned can to the method that sulphur positive electrode is modified Improve the electric conductivity of lithium-sulfur cell or improve its cycle performance, but the energy density of the lithium-sulfur cell for obtaining is reduced, that is, Say, this method being modified to sulphur positive electrode can not on the whole improve the performance of lithium-sulfur cell.
Therefore, a kind of positive electrode that can on the whole improve sulphur lithium battery performance is now needed badly.
The content of the invention
Goal of the invention：The first object of the present invention is to provide a kind of with superior electric conductivity, cycle performance and higher The sulphur anode material of lithium battery of the phosphoric acid zirconium titanium of service life and energy density；The second object of the present invention is the offer positive pole The preparation method of material.
Technical scheme：The sulphur anode material of lithium battery of phosphoric acid zirconium titanium of the present invention, including mass ratio is (0.001～2)：1： The conductive additive of (0.1～1), sulphur and zircomium-tiatnium phosphate, the sulphur is carried in conductive additive and zircomium-tiatnium phosphate.
Zircomium-tiatnium phosphate is a stratiform multifunctional material, is used as ion-exchanger, catalyst and adsorbent etc., stratiform phosphorus Sour zirconium titanium does not only have the general character of lamellar compound, and preparation is easy, crystalline form is excellent, heat endurance is high, layer structure is stable, have larger Specific surface area, high ion exchange capacity and layer surface contain substantial amounts of-OH groups, can be modified as needed；This Outward, it has solid acid catalysis function, and can occur the excellent specific property such as selective in catalytic reaction process.
Therefore, the present invention adopts sulfur granules, conductive additive and zircomium-tiatnium phosphate.Zircomium-tiatnium phosphate used as carrier, imitate by its stratiform The self-discharge processes of battery should be able to effectively be suppressed, and sulfur granules are carried in the zircomium-tiatnium phosphate, due to zircomium-tiatnium phosphate uniqueness Layer structure tightly wrapped sulfur granules, can effectively suppress its electric discharge intermediate product polysulfide dissolving, improve The cycle performance of lithium-sulfur cell；The addition of conductive additive improves the electric conductivity of positive electrode.Preferably, conductive additive, The mass ratio of sulphur and zircomium-tiatnium phosphate is (0.005～0.2)：1：(0.1～0.4).
Furtherly, the chemical formula of zircomium-tiatnium phosphate is Ti3xZr3-3x(PO4)4, X=0.01～0.99, preferably can for 0.1～ 0.7；Conductive additive at least may include the one kind in conductive carbon black, carbon fiber, acetylene black, Graphene or CNT.
The method that the present invention prepares the sulphur anode material of lithium battery of phosphoric acid zirconium titanium, comprises the steps：
(1) preparation of zircomium-tiatnium phosphate：3X in molar ratio：(3-3X)：4 weigh titanium salt, zirconates and phosphorus-containing compound, by titanium Salt, zirconates are dissolved in 1-50 times of deionized water, add phosphorus-containing compound, are adjusted pH3～9 and are reacted after 1～4h, stand 10～20h, Then filter, wash, be dried；
(2) prepared by positive electrode：Solvent is added to grind 1～20h conductive additive, sulphur and zircomium-tiatnium phosphate in mass ratio After be dried, regrind 10～600min, then calcine at 100～160 DEG C under an inert gas after 2～20h again 280～ 320 DEG C of 1～19h of calcining, are cooled to room temperature.
The present invention be dried after 1～20h using first being ground, and regrinds the mode of 10～600min, can effectively eliminate the The caking phenomenon that primary drying is produced；In calcining, 2～20h is first calcined under the conditions of 100～160 DEG C, permeate can sulphur To in zircomium-tiatnium phosphate, after again under the conditions of 280～320 DEG C calcine 1～19h, can further remove zircomium-tiatnium phosphate adsorption Sulphur.
Furtherly, the titanium salt for adopting in preparation method of the invention at least may include titanium sulfate, titanyl sulfate or tetrachloro Change the one kind in titanium；Zirconates at least may include the one kind in zirconium oxychloride, zirconium sulfate or zirconium nitrate；Phosphorus-containing compound at least can be wrapped Include the one kind in phosphoric acid, ammonium dihydrogen phosphate or diammonium hydrogen phosphate；Solvent at least may include methyl alcohol, ethanol, propyl alcohol, N- methylpyrroles One kind in alkanone or dimethylformamide.
Beneficial effect：Compared with prior art, remarkable advantage of the invention is：The positive electrode first charge-discharge capacity is all It is strong in 1000mAh/g or so, electric conductivity, after cycle charge-discharge 20 times, substantially remain in 700mAh/g or so, cyclical stability It is good, with higher service life and energy density；Additionally, the preparation process is simple of the positive electrode, synthesis condition are gentle, anti- Short, low cost between seasonable, and the zircomium-tiatnium phosphate powder granularity prepared is uniform, particle diameter is little, pattern is regular single, can be conducive to Improve the specific capacity and cyclical stability of the positive electrode.
Description of the drawings
Fig. 1 is the electron microscope of zircomium-tiatnium phosphate prepared by the embodiment of the present invention 1.
Specific embodiment
Technical scheme is described further with reference to embodiment.
Embodiment 1
(1) preparation of zircomium-tiatnium phosphate：2.7mol eight is hydrated into zirconium oxychloride and 0.3mol titanium tetrachlorides are added sequentially to In 330mol deionized waters, stirring 1h obtains clear liquid, is subsequently adding the 85% of 2mol phosphoric acid and 40% biphosphate of 0.575kg Aqueous ammonium；Above-mentioned reaction mass is stirred and add after 1h after ammoniacal liquor regulation pH5, then PH6.5, stirring reaction are adjusted with monoethanolamine 2h, stands 15h, filters product after stirring, is washed with a large amount of deionized waters, and filter cake is dried at 120 DEG C, and grinding obtains final product white Color powder zircomium-tiatnium phosphate, as shown in Figure 1.Wherein, titanium tetrachloride, eight hydration zirconium oxychlorides and phosphorus-containing compound (phosphoric acid and phosphorus Acid dihydride ammonium) mol ratio be 0.3:2.7:4.
(2) prepared by positive electrode：By 0.14g conductive blacks, 0.07g CNTs, 17g sulphur powders, 2.86g zircomium-tiatnium phosphates (wherein, the mass ratio of conductive additive, sulphur powder and zircomium-tiatnium phosphate is 0.012:1:0.168), 30g methyl alcohol and 5g ethanol, Mechanical ball mill 3h under 350rpm, heats the mixture for obtaining 12h and dries at 60 DEG C, then ball milling 20min is obtained under 250rpm To grey black mixture, the grey black mixture is placed in into atmosphere furnace, under inert nitrogen gas protection, is first forged at 150 DEG C 10h is burnt, 300 DEG C of calcining 2h are then warmed up to, room temperature taking-up is subsequently cooled to, then is crushed to D50 with ball mill and is obtained for 9um Composite positive pole.
The button cell of the lithium sulfur battery anode material assembling that embodiment 1 is provided, test it in 0.2C, 0.5C, 1C and The specific capacity that circulation under 2C different multiplyings is 20 times is respectively 780,700,680,600mAh/g, all with higher specific capacity, High rate performance is very good.
Embodiment 2
(1) preparation of zircomium-tiatnium phosphate：1.5mol Zirconium bis(sulfate) tetrahydrates and 1.5mol titanium sulfates are added sequentially to into 290mol In deionized water, stirring 1h obtains clear liquid, is subsequently adding 40% ammonium dihydrogen phosphate aqueous solution of 1.15kg；Above-mentioned reaction mass is stirred Mix and add after 2h after ammoniacal liquor regulation pH7, be stirred for reacting 2h, stand 10h, filter product after stirring, be washed with deionized, Filter cake is spray-dried at 125 DEG C, grinding obtain final product white powder zircomium-tiatnium phosphate, wherein, titanium sulfate, Zirconium bis(sulfate) tetrahydrate and The mol ratio of ammonium dihydrogen phosphate is 1.5:1.5:4；
(2) prepared by positive electrode：By 0.2g Graphenes, 17g sulphur powders, 2.86g zircomium-tiatnium phosphates (Graphene, sulphur powder and phosphoric acid The mass ratio of zirconium titanium is 0.012:1:0.17) with 30g ethanol, mechanical ball mill 8h under 350rpm, by the mixture for obtaining 65 Baking oven heating 15h drying at DEG C, then at 200 rpm ball milling 30min obtains grey black mixture, by the grey black mixture Atmosphere furnace is placed in, under inert gas argon gas shielded, first 8h is calcined at 155 DEG C, be then warmed up to 305 DEG C of calcining 3h, subsequently Room temperature is cooled to, then D50 is crushed to ball mill and obtain composite positive pole for 8um.
Embodiment 3
(1) preparation of zircomium-tiatnium phosphate：Take the nitric hydrate zirconiums of 0.5mol five and 2mol titanyl sulfates, 0.5mol titanium tetrachlorides according to Secondary to be added in 290mol deionized waters, stirring 1h obtains clear liquid, is subsequently adding 40% ammonium dibasic phosphate aqueous solution of 1.32kg；Will Add monoethanolamine to adjust after pH6.7 after above-mentioned reaction mass stirring 2h, be stirred for reacting 4h, 16h is stood, by product mistake after stirring Filter, is washed with deionized, and filter cake is spray-dried at 120 DEG C, and grinding obtains final product white powder zircomium-tiatnium phosphate, wherein, titanium The mol ratio of salt, five nitric hydrate zirconiums and diammonium hydrogen phosphate is 2.5:0.5:4；
(2) prepared by positive electrode：By 0.3g CNTs, 17g sulphur powders, 2.6g zircomium-tiatnium phosphates (CNT, sulphur powder and phosphorus The mass ratio of sour zirconium titanium is 0.18:1:0.15) with 30gN- methyl pyrrolidones (NMP), 5g propyl alcohol, the mechanical ball under 350rpm Mill 10h, by the mixture for obtaining heating 15h drying is vacuumized at 65 DEG C, then at 200 rpm ball milling 30min obtains grey black Mixture, is placed on atmosphere furnace, under inert nitrogen gas protection, first 5h is calcined at 148 DEG C, is then warmed up to 300 DEG C Calcining 2h, is subsequently cooled to room temperature, then is crushed to D50 with ball mill to obtain composite positive pole for 7um.
Embodiment 4
(1) preparation of zircomium-tiatnium phosphate：Take the nitric hydrate zirconiums of 2.4mol five, 0.5mol zirconium oxychlorides and 0.1mol titanium tetrachlorides In being added sequentially to 290mol deionized waters, stirring 1h obtains clear liquid, is subsequently adding 40% ammonium dihydrogen phosphate aqueous solution of 0.575kg With 0.5mol phosphoric acid；Above-mentioned reaction mass is stirred and add after 2h after diethanol amine regulation pH6.5, be stirred for reacting 4h, stood 16h, filters product after stirring, is washed with deionized, and filter cake is spray-dried at 135 DEG C, and grinding obtains final product white powder Shape zircomium-tiatnium phosphate, wherein, the mol ratio of titanium tetrachloride, zirconates and phosphorus-containing compound is 0.1:2.9:4.
(2) prepared by positive electrode：By 0.17g acetylene blacks, 17g sulphur powders, 2.95g zircomium-tiatnium phosphates (acetylene black, sulphur powder and phosphoric acid The mass ratio of zirconium titanium is 0.01:1:0.174) with 30g dimethylformamides (DMF), mechanical ball mill 10h under 350rpm, will To mixture heating 15h drying is vacuumized at 85 DEG C, then at 200 rpm ball milling obtains grey black mixture for 20 minutes, will It is placed in atmosphere furnace, under inert nitrogen gas protection, first 10h is calcined at 155 DEG C, is then warmed up to 300 DEG C of calcining 2.5h, It is subsequently cooled to room temperature, then D50 is crushed to ball mill to obtain zircomium-tiatnium phosphate-sulphur-acetylene black composite positive pole material for 10um.
Experimental example 5
The lithium sulfur battery anode material that above-described embodiment 1-4 is obtained and conductive agent Super P and binding agent polyvinylidene fluoride Alkene is 80 in mass ratio:10:10 ratio is placed in the N-methyl pyrrolidones of 6 times of amounts, grinds 3h, is coated on aluminium foil, is applied Cloth thickness is 100 μm.The aluminium foil of mixture is coated with after vacuum drying 24h at 60 DEG C, be cut to diameter 1.6cm by what is obtained Round positive plate.In the glove box full of argon gas, with lithium piece as negative pole, it is with CELGARD2400 microporous polypropylene films Barrier film, then add containing 1%LiNO3Molar concentration for the double trifluoromethanesulfonimide lithiums of LiTFSI of 1mol/L, (solvent is Isopyknic glycol dimethyl ether DME and DOX DOL) it is electrolyte, it is assembled with the positive plate for obtaining, Obtain lithium sulphur button cell.
The present invention has investigated the performance of this lithium-sulfur cell.Wherein, discharge and recharge is interval for 1.7-2.8V, charging and discharging currents density For 0.2C (1C=1675mAh/g).The specific discharge capacity of above-mentioned lithium-sulfur cell is as shown in table 1.
Table 1：
Shown by the result of table 1, the button cell of the lithium sulfur battery anode material assembling that the present invention is provided, its first charge-discharge , all in 900～1200mAh/g or so, this explanation initial discharge capacity is very high, after cycle charge-discharge 20 times, is maintained at for capacity More than 650mAh/g, cyclical stability is very good.
Embodiment 6
(1) preparation of zircomium-tiatnium phosphate：2.97mol zirconium sulfates and 0.03mol titanium tetrachlorides are added sequentially to into 300mol In ionized water, stirring 1h obtains clear liquid, is subsequently adding 40% ammonium phosphate solution of 2.03kg；Above-mentioned reaction mass is stirred after 1h Add monoethanolamine to adjust after pH9, be stirred for reacting 1h, stand 20h, filter product after stirring, washed with a large amount of deionized waters, Filter cake is dried at 120 DEG C, grinding obtains final product white powder zircomium-tiatnium phosphate, wherein, titanium tetrachloride, zirconium sulfate and ammonium phosphate Mol ratio is 0.03:2.97:4.
(2) prepared by positive electrode：By 0.085g carbon fibers, 17g sulphur powders, 1.7g zircomium-tiatnium phosphates (conductive additive, sulphur powder and The mass ratio of zircomium-tiatnium phosphate is 0.005:1:0.1), 18.785g methyl alcohol, mechanical ball mill 10h under 350rpm, by the mixing for obtaining Thing heats 12h drying at 60 DEG C, then ball milling 300min obtains grey black mixture under 250rpm, by the grey black mixture Atmosphere furnace is placed in, under inert gas argon gas shielded, first 20h is calcined at 100 DEG C, be then warmed up to 315 DEG C of calcining 1h, subsequently Room temperature taking-up is cooled to, then D50 is crushed to ball mill and obtain zircomium-tiatnium phosphate-sulphur-carbon fiber composite positive pole for 9um.
Embodiment 7
(1) preparation of zircomium-tiatnium phosphate：By 0.9mol zirconium sulfates and 2.1mol titanium tetrachlorides be added sequentially to 310mol go from In sub- water, stirring 1h obtains clear liquid, is subsequently adding 40% ammonium phosphate solution of 2.03kg；Above-mentioned reaction mass is stirred and add after 1h Enter diethanol amine to adjust after pH5, then PH7 adjusted with monoethanolamine, be stirred for reacting 2h, stand 20h, filter product after stirring, Washed with a large amount of deionized waters, filter cake is dried at 120 DEG C, grinding obtains final product white powder zircomium-tiatnium phosphate, wherein, four chlorinations The mol ratio of titanium, zirconium sulfate and ammonium phosphate is 2.1:0.9:4.
(2) prepared by positive electrode：By 0.17g CNTs, 17g sulphur powders, 0.51g zircomium-tiatnium phosphates (conductive additive, sulphur powder And the mass ratio of zircomium-tiatnium phosphate is 0.01:1:0.3), 176.8g methyl alcohol, mechanical ball mill 20h under 350rpm, by the mixing for obtaining Thing heats 12h drying at 60 DEG C, then ball milling 10min obtains grey black mixture under 250rpm, by the grey black mixture Atmosphere furnace is placed in, under inert nitrogen gas protection, first 2h is calcined at 160 DEG C, be then warmed up to 280 DEG C of calcining 19h, subsequently Room temperature taking-up is cooled to, then D50 is crushed to ball mill and obtain zircomium-tiatnium phosphate-sulphur-carbon/carbon nano tube compound anode material for 9um Material.
Embodiment 8
(1) preparation of zircomium-tiatnium phosphate：By 0.3mol zirconium sulfates and 2.97mol titanium tetrachlorides be added sequentially to 930mol go from In sub- water, stirring 1h obtains clear liquid, is subsequently adding 40% ammonium phosphate solution of 2.03kg；Above-mentioned reaction mass is stirred and add after 1h Enter ammoniacal liquor to adjust after pH3, stirring reaction 2h stands 20h, filters product after stirring, is washed with a large amount of deionized waters, by filter cake Dry at 120 DEG C, grinding obtains final product white powder zircomium-tiatnium phosphate, wherein, the mol ratio of titanium tetrachloride, zirconium sulfate and ammonium phosphate For 2.97:0.03:4.
(2) prepared by positive electrode：By 0.34g CNTs, 17g sulphur powders, 6.8g zircomium-tiatnium phosphates (conductive additive, sulphur powder And the mass ratio of zircomium-tiatnium phosphate is 0.2:1:0.4), 48.28g methyl alcohol, mechanical ball mill 1h under 350rpm, by the mixture for obtaining 12h drying is heated at 60 DEG C, then ball milling 600min obtains grey black mixture under 250rpm, and the grey black mixture is put In atmosphere furnace, under inert nitrogen gas protection, first 10h is calcined at 100 DEG C, be then warmed up to 320 DEG C of calcining 8h, it is subsequently cold But take out to room temperature, then D50 is crushed to ball mill and obtain zircomium-tiatnium phosphate-sulphur-carbon/carbon nano tube compound anode material for 9um.
Positive electrode obtained in embodiment 6-8 is carried out into performance detection in the way of embodiment, the result of the test of acquisition is such as Shown in table 2.
Table 2：
Shown by the result of table 2, the button cell of the lithium sulfur battery anode material assembling that the present invention is provided, its first charge-discharge , all in 900～1200mAh/g or so, this explanation initial discharge capacity is very high, after cycle charge-discharge 20 times, is maintained at for capacity More than 650mAh/g, cyclical stability is very good.
Embodiment 9
Basic step is same as Example 1, and difference is the mass ratio of conductive additive, sulphur and zircomium-tiatnium phosphate, tool Body is：(0.001:1:0.1)、(0.005:1:0.1)、(0.015:1:0.2)、(1:1:1)、(2:1:0.5)、(2.5:1: 0.05)、(2:1:1.5), obtained positive electrode respectively is carried out into performance detection, the result of acquisition is as shown in table 3.
Table 3：
By table 3, the positive electrode prepared using the mass ratio of the present invention, its initial discharge capacity is very high, circulation After discharge and recharge 20 times, stability is strong；And positive electrode prepared by 6-7 groups, because sulfur-bearing is few, specific capacity is low.

Claims (10)

1. a kind of sulphur anode material of lithium battery of phosphoric acid zirconium titanium, it is characterised in that：The positive electrode is including mass ratio (0.001～2)：1：The conductive additive of (0.1～1), sulphur and zircomium-tiatnium phosphate, the sulphur is carried on conductive additive and basic zirconium phosphate The inside and surface of titanium.
2. the sulphur anode material of lithium battery of phosphoric acid zirconium titanium according to claim 1, it is characterised in that：The conductive addition The mass ratio of agent, sulphur and zircomium-tiatnium phosphate is (0.005～0.2)：1：(0.1～0.4).
3. according to right 1 phosphoric acid zirconium titanium sulphur anode material of lithium battery, it is characterised in that：The chemistry of the zircomium-tiatnium phosphate Formula is Ti3xZr3-3x(PO4)4, X=0.01～0.99.
4. according to right 3 phosphoric acid zirconium titanium sulphur anode material of lithium battery, it is characterised in that：X=0.1～0.7.
5. the sulphur anode material of lithium battery of phosphoric acid zirconium titanium according to claim 1, it is characterised in that：The conductive additive At least include the one kind in conductive carbon black, carbon fiber, acetylene black, Graphene or CNT.
6. a kind of method for preparing the sulphur anode material of lithium battery of phosphoric acid zirconium titanium described in any one of claim 1-5, its feature It is to comprise the steps：
(1) preparation of zircomium-tiatnium phosphate：3X in molar ratio：(3-3X)：4 weigh titanium salt, zirconates and phosphorus-containing compound, by titanium salt, zirconium Salt is dissolved in 1-50 times of deionized water, adds phosphorus-containing compound, and it is 3～9 1～4h of reaction to adjust pH, after standing 10～20h, Filter, wash, be dried；
(2) prepared by positive electrode：Conductive additive, sulphur and zircomium-tiatnium phosphate are mixed in mass ratio, adds 1～10 times of solvent Grinding 1～20h after be dried, regrind 10～600min, then under an inert gas at 100～160 DEG C calcine 2～20h It is cooled to room temperature in 280～320 DEG C of 1～19h of calcining again afterwards.
7. the method for preparing the sulphur anode material of lithium battery of phosphoric acid zirconium titanium according to claim 6, it is characterised in that：Step (1) in, the titanium salt at least includes the one kind in titanium sulfate, titanyl sulfate or titanium tetrachloride.
8. the method for preparing the sulphur anode material of lithium battery of phosphoric acid zirconium titanium according to claim 6, it is characterised in that：Step (1) in, the zirconates at least includes the one kind in zirconium oxychloride, zirconium sulfate or zirconium nitrate.
9. the method for preparing the sulphur anode material of lithium battery of phosphoric acid zirconium titanium according to claim 6, it is characterised in that：Step (1) in, the phosphorus-containing compound at least includes the one kind in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate.
10. the method for preparing the sulphur anode material of lithium battery of phosphoric acid zirconium titanium according to claim 6, it is characterised in that：Step Suddenly in (2), the solvent at least includes the one kind in methyl alcohol, ethanol, propyl alcohol, 1-METHYLPYRROLIDONE or dimethylformamide.
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