SE544708C2 - Manufacture of a titanium dioxide bronze material for a battery electrode - Google Patents
Manufacture of a titanium dioxide bronze material for a battery electrodeInfo
- Publication number
- SE544708C2 SE544708C2 SE2050954A SE2050954A SE544708C2 SE 544708 C2 SE544708 C2 SE 544708C2 SE 2050954 A SE2050954 A SE 2050954A SE 2050954 A SE2050954 A SE 2050954A SE 544708 C2 SE544708 C2 SE 544708C2
- Authority
- SE
- Sweden
- Prior art keywords
- titanium dioxide
- bronze
- battery
- precipitate
- electrode material
- Prior art date
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 43
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 229910000906 Bronze Inorganic materials 0.000 title claims description 26
- 239000010974 bronze Substances 0.000 title claims description 26
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000000243 solution Substances 0.000 claims abstract description 34
- 239000002244 precipitate Substances 0.000 claims abstract description 27
- 239000007772 electrode material Substances 0.000 claims abstract description 23
- 229910010270 TiOCl2 Inorganic materials 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 229940061720 alpha hydroxy acid Drugs 0.000 claims abstract description 7
- 150000001280 alpha hydroxy acids Chemical class 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000004020 conductor Substances 0.000 claims description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910010455 TiO2 (B) Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- OFHCOWSQAMBJIW-AVJTYSNKSA-N alfacalcidol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)C[C@H](O)C1=C OFHCOWSQAMBJIW-AVJTYSNKSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000036961 partial effect Effects 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910003074 TiCl4 Inorganic materials 0.000 claims 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 11
- 230000008030 elimination Effects 0.000 abstract description 2
- 238000003379 elimination reaction Methods 0.000 abstract description 2
- 230000002829 reductive effect Effects 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- -1 titanium ions Chemical class 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000001530 Raman microscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910010251 TiO2(B) Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- GIMXAEZBXRIECN-UHFFFAOYSA-J 2-hydroxyacetate;titanium(4+) Chemical compound [Ti+4].OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O GIMXAEZBXRIECN-UHFFFAOYSA-J 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920006370 Kynar Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a method for manufacturing a battery including a battery and electrode material, the method comprising the steps of a) providing an aqueous solution comprising TiOCl2, HC1, and an alpha-hydroxy acid, b) increasing the pH of the solution until a precipitate is obtained, wherein the temperature is above 0 °C and below 55 °C and c) calcining the obtained precipitate at a temperature in the interval 300-450 °C during a time range of 5 minutes to 48 hours to obtain a calcined material comprising the titanium dioxide in bronze form. Advantages are the elimination of high pressure and high temperature as in the prior art. The method is further faster and give material with a substantially reduced surface area per weight unit, which is desired for batteries.
Description
MANUFACTURE OF A TITANIUM DIOXIDE BRONZE MATERIAL FOR A BATTERY ELECTRODE Technical Field The invention relates to a method for manufacturing a battery comprising at least one titanium dioxide in bronze form. The titanium dioxide in bronze form as well as an electrode and the battery both comprising the titanium dioxide in bronze form are encompassed as well.
Background In the prior art there are disclosed methods of manufacturing titanium dioxide bronze material, which can be used for in the manufacture of a battery. The known methods according to the prior art either requires a) an expensive and complicated hydrothermal process step operating at elevated temperature, pressure and high alkalinity, with a limited scale up capacity of the pressure vessels, or b) a very high temperature process step, greater than approx. 800°C to make a material comprising titanium dioxide in bronze form or c) making TiO2(B) from a titanium glycolate precursor which generally involves use of dangerous oxidizers such as hydrogen peroxide.
For batteries, some polymorphs of TiO2 are more desirable whereas others are undesirable. Anatase is undesirable as it generally loses half of its capacity relative to the first few cycles, unlike bronze, which retains most of its capacity after an initial approx. 20% loss on first cycle.
Thus, the bronze polymorph can more readily achieve high capacities than anatase.
For the bronze polymorph TiO2 (B) the theoretical specific capacity is about 335 mAh/g, when used in an electrode in a lithium battery.
Summary It is an object of the present invention to alleviate at least some of the problems in the prior art and to provide a method for manufacturing a material comprising titanium dioxide in bronze form which is suitable for manufacturing batteries.
It has been discovered that it is possible isolate a titanium dioxide material to minimize the formation of anatase, by a process of simple mixing of chemicals followed by a simple precipitation reaction in acidic conditions at low temperature and atmospheric pressure without need for a containment vessel.
The current invention gives a huge difference from the three routes described above, which according to the state of the art were the only realistic ways to making materials comprising titanium dioxide in bronze form.
In a first aspect there is provided a method for (B), material for a battery electrode material, manufacturing a TiO2 titanium dioxide bronze the method comprising the steps of: a)providing an aqueous solution comprising TiOCl2, HCl, and an alpha-hydroxy acid, b) increasing the pH of the solution until a precipitate is obtained, wherein the ltemperature is above 0 °C and below 55 °C, and c)calcining the obtained precipitate during a time range of 5 minutes to 48 hours at a temperature in the interval 300-450 °C to obtain a calcined material comprising the titanium dioxide in bronze form.
A second aspect is related to a titanium dioxide bronze electrode material for a battery manufactured according to the method.
A third aspect is related to a battery having an electrode comprising a titanium dioxide bronze material manufactured according to the method.
Advantages of the invention over the prior art include the elimination of either pressure vessels or high temperature calcination and thus is advantageous over prior art methods also from a cost, time, and scaling point of view. A further advantage is that it is safer compared to the use of hydrogen peroxide in the third method c).
The method according to the present invention further has the advantages that it can allow faster more efficient processing of the ingredients into titanium dioxide in bronze form compared to material made by a hydrothermal method according to the state of the art. This gives lower energy consumption during manufacture as well as lower cost and lower environmental impact.
Yet another advantage is that the method allows manufacture of a titanium dioxide in bronze form with a substantially reduced surface area compared to the prior art materials, giving that it has less side reactions in batteries than those caused by the materials manufactured by the hydrothermal pathway according to the prior art. These substantial advantages can be achieved without the energy consuming and costly high temperature step according to the prior art.
Brief description of the Drawings Fig 1 shows an experimental result as described more in detail in the experimental section. Fig 1 shows the specific capacity of a battery cell comprising the electrode material manufactured according to the invention, when the battery is cycled a number of times. In fig 1 it can be seen that for a battery comprising the material made according to the invention the capacity at cycle 3 was approximately 92 mAh/g at C/10 and an approximately stable capacity of 80 mAh/g.
Fig 2 shows a result from the same cell as in fig 1. In fig2 the specific capacity as well as the Coulombic efficiency can be seen as a function of the number of cycles of the battery. The Coulombic efficiency is the lower line. It can be seen that the Coulombic efficiency levelled out at 100% after about 5-cycles out to 250 cycles at C/ Fig 3 shows a schematic drawing of a battery according to the invention comprising a working anode (1), a counter electrode (2), a separator (3), a lower casing lO (4), (5), In this particular embodiment the working anode (l) an upper casing and a gasket (6). comprises electrode material according to the invention made by the method according to the invention.
Fig 4 shows a flow chart of the method according to the present invention.
Detailed description The following detailed description discloses by way of examples details and embodiments by which the invention may be practised.
Bronze as used in the claims refers to titanium dioxide in bronze form. The term bronze includes both titanium dioxide in bronze form and bronze-like material. Bronze or bronze-like means materials that have the TiO2(B) crystal structure that is difficult to distinguish from bronze using XRD or Raman spectroscopy but is distinct from the XRD pattern or Raman spectra of anatase. Further bronze-like materials can have components of the material that are defected bronze, in the crystallographic sense and may also contain elements other than titanium and oxygen. The aqueous solution in steps a) and b) of the method is in one embodiment a clear solution before the precipitate is formed, although there may be cases where there are additives and/or impurities so that it is not clear. A “clear solution' is defined as being nearly or completely transparent to visible light with little or no detectable cloudiness or scattering of visible light by undissolved titanic acid and may be lO determined by shining a visible light laser through the solution until it passes straight through the solution with little to no detectable scattering of visible light from within the solution to the naked eye. Alternately in the absence of a laser light source it may be detected in practise when ordinary 12 point printed text is resolved through a lOcm path- length of the solution held in a glass pipe. “Suspension' as used throughout the description are solid particles in a liquid medium. For a suspension the particles are at least partially so large that they settle after some time due to gravity. The solid particles in the suspension can be for instance a precipitate.
*Wt%' denotes percentage by weight. All percentages and ratios are calculated by weight unless otherwise clearly stated.
In a first aspect there is provided a method for (B), material for a battery electrode material, manufacturing a TiO2 titanium dioxide bronze the method comprising the steps of: a)providing an aqueous solution comprising TiOCl2, HCl, and an alpha-hydroxy acid, b) increasing the pH of the solution until a precipitate is obtained, wherein the temperature is above O °C and below 55 °C, and c)calcining the obtained precipitate during a time range of 5 minutes to 48 hours at a ltemperature in the interval 300-450 °C to obtain a calcined material comprising the titanium dioxide in bronze form.
The aqueous solution comprising TiOCl2 can be provided in several ways, in one embodiment, it is provided by at least partial hydrolysis of TiCl In another embodiment the aqueous solution comprising TiOCl2 is provided by dissolving at least one titanic acid with the general formula TiOX(OH)44X, wherein X is 0 or l, in an aqueous solution comprising at least one compound and selected from the group consisting of TiOCl2, TiCl@ HCl so that a clear solution is obtained, while keeping the temperature below 30 °C. In one embodiment, the at least one titanic acid is made from TiOCl2 by addition of an aqueous solution of a base until precipitation. The latter approach has the advantage that the process is easier to control, in particular in large scale. More in particular it is possible to measure and control the acidity with high accuracy. The acidity is the ability to donate protons in an aqueous solution, i.e. the acidity is the amount of acids.
In one embodiment, the obtained precipitate is washed in water between steps b) and c). The calcination is carried out so that the organic material including the alpha-hydroxy acid is removed. Further the calcination should be carried out so that a rearrangement occurs in the material in such a way that the fraction of anatase is minimized and the fraction of titanium dioxide in bronze form is This is normally done by choosing a lower maximized. temperature in the interval 300-450 °C together with a llonger calcination time, or a higher temperature in the interval 300-450 °C together with a shorter calcination time. A skilled person can in the light of the description and the appended examples choose a suitable temperature and time for the calcination. A time range for the calcination is in one embodiment 5 minutes to 48 hours.
In one embodiment, the method is carried out at a pressure p being ambient pressure f20%. In a variant embodiment, the method is carried out at ambient pressure. Ambient pressure is the atmospheric pressure at which the method is carried out.
In one embodiment, the pH of the solution in step b) of the method is increased by addition of NaOH.
In one embodiment, the at least one alpha hydroxy acid is citric acid.
In one embodiment the aqueous solution provided in step a) is a clear solution as defined above. This has the advantage that it is ensured that any reaction giving the TiOCl2 is more complete.
Between steps b) and c), it is possible to let the precipitate be dried and optionally ground.
In one embodiment, the obtained precipitate in step b) is separated from the remaining liquid between steps b) and c). no transition metal ions except or b).
In one embodiment, titanium ions are added in step a) In one embodiment, at least one type of ions selected from the group consisting of Naf, Kf, Rbf, Cs*, Znß and La* are added at any point before step c). Such ions have a stabilizing effect, but too high concentration of these ions can reduce the efficiency of the material in a battery. Such ions have the effect of delaying or decreasing the transition to anatase. Lighter ions are preferred in order to make the final for instance Na is material more lightweight. Thus, preferred over Cs. In one embodiment, Nb-ions are added at any point before step b) and/or before the calcination. Suitably Nb-ions could be added up to an amount corresponding to a ratio of 8:1 calculated as the ratio between the weight of Titanium ions to Niobium ions. The Nb-ions have the advantage of improving the conductivity.
In one embodiment the pH in step b) is increased also after the precipitate is obtained and wherein the pH is increased to a value in the range 7-10. This has the effect that the charge of certain groups of the titanium dioxide is reversed to become negative so that positive ions such as Na*-ions are attracted to the material.
In order to obtain an electrode material for use in a battery, in one embodiment, of the method at least one conducting material and least one binder is added to the calcined material to obtain an electrode material for a battery in and/or after step c). In one embodiment the conducting material is carbon black. In one embodiment the electrode material comprises about 90 wt% of TiO2 bronze, 6-7 wt% carbon black and 4-wt% binder.
In one embodiment a conducting material and/or a precursor to a conducting material is added before the calcination step. Such a conducting material should then be able to withstand the calcination. A precursor of a conducting material shall break down to a conducting material during the calcination. In one embodiment the conducting material is added after the calcination step. In one embodiment the binder is added before the calcination step. However, as most binders would not be able to withstand the calcination and/or would be oxidized during the calcination in many cases the binder is added after the calcination. In one embodiment the calcined material is mixed with binder and conducting material after the calcination. at least one precursor for a conducting material is added before the calcination to obtain an electrode material for a battery In one embodiment the at least one conducting material, the least one binder and the calcined material are mixed in a slurry.
In one embodiment the content of the calcined material in the electrode material is 70-90 wt%.
In one embodiment the BET specific surface area of the calcined material according to ISO 9277 is in the range of 2-30 m?/g.According to the second aspect there is provided an electrode material for a battery manufactured according to the method.
In one embodiment of the second aspect the electrode material comprises a) 70-90 wt % of calcined titanium dioxide bronze having a BET specific surface area according to ISO 9277 in the range 2-30 m?/g, and b) - 10 wt% of a mixture of i) a conducting material and ii) a binder.
In one embodiment of the second aspect the wt% ratio between the conducting material and the binder is in The wt% the range 1:1 to 7:3. ratio is calculated by dividing the wt% of conducting material with the wt% of the binder. The fraction of conducting material is adapted so that sufficient conduction is obtained. The fraction of binder is selected so that sufficient binding and integrity is obtained without the fraction of binder being too high.
In one embodiment of the second aspect the conducting material is carbon black.
In embodiment of the second aspect the titanium dioxide bronze comprises at least one type metal ion of selected from m metal group of sodium, potassium, caesium, rubidium, zinc, lanthanum, and tin. Such metal ions have the advantage of giving a higher fraction of titanium dioxide in bronze form by inhibiting the transition to anatase during the manufacturing process.In the third aspect there is provided a battery having an electrode comprising a titanium dioxide bronze material manufactured according to the method.
In one embodiment of the third aspect the BET specific surface area according to ISO 9277 is in the range 2- 30 m?/g. This specific surface area is relatively low compared to other similar materials and such a small specific surface area in a battery and a battery electrode material has the advantage that various side reactions are suppressed.
Examples The invention is further described by the following non-limiting examples.
Example 1 The starting materials were a commercial TiOClsolution, NaOH and citric acid and deionized water.
The TiOCl2 solution was received with composition of approximately 35-26% TiOCl2, hydrochloric acid 22-24% and water 40-43%. The measured density of the TiOClsolution at 20°C was 1.5605 f 0.001O g.cm*. 5.01g of water was added to 10.02g TiOCl2 solution with stirring and cooling to below 25 °C to obtain a diluted TiOCl2 solution. To the diluted TiOCl2 solution was added 43.85g of a solution comprising 10% by weight NaOH in water, with stirring and cooling to maintain a temperature below 25 °C. This resulted in a suspension of white titanium-containing precipitate of approximately pH 5. To this suspension was added 23.g of TiOCl2 solution, keeping the temperature below°C until the solution became completely transparent.
To this transparent or “clear” solution 0.759 g ofcitric acid was added under stirring until the citric acid was dissolved. To this solution 95.88g of 10% NaOH solution was added resulting in a second suspension of titanium bearing precipitate at approximately pH 4. Stirring was continued for approximately 15 minutes after the last addition of 10% NaOH.
Approximately 100 ml of the second suspension was then placed into two 50 ml centrifuge tubes and centrifuged and decanted multiple times for 2 minutes at 3000 rcf (relative centrifugal force), each followed by addition of deionized water and resuspension after each decantation. This was repeated until the NaCl content was substantially decreased obtaining a washed precipitate. The washed precipitate was then dried in air until the material was dry and was ground to uniformity using an agate mortar and pestle to obtain a fine powder. The fine powder was then subject to analysis by Raman microscopy and X-ray powder diffraction. These analyses indicated the fine powder was substantially free of anatase. Approximately 0.3g of the fine powder was then heated in air at 350 °C for one hour to obtain a calcined powder sample. The calcined powder sample was then subject to analysis using a Raman spectrometer, yielding a spectrum indicating a high fraction of anatase. The sample was then analysed by energy dispersive x-ray analysis The (EDX) using a Zeiss scanning electron microscope. atomic titanium to sodium ratio (Ti/Na) was determined to be 4.9f0.
Example 1bApproximately 5 g of the washed precipitate of Example 1 was suspended in an excess of 0.1 M HCl solution and stirred overnight to replace any Na in the titanium dioxide with H ions to obtain a suspension of acid exchanged titanium dioxide. The acid exchanged titanium dioxide was then washed by repeated centrifugation and decantation to obtain a neutral suspension of washed, acid-exchanged titanium dioxide at pH 5-6. The. The washed acid-exchanged titanium dioxide was then air dried, ground and found to have a tap density of 0.8 gcm*. The sample was then heated at100% °C for 1 hour and its phase determined as close to anatase.
Example 1c 2.974g of powder from example lb was added to a mixture of 0.1M 37.8g NaOH and 61.3g deionized water. The mixture was magnetically stirred for 15 minutes and then transferred to an oven for 1 hour, the temperature being 40°C at the end, and without stirring. The pH after removal from the oven was near neutral. The sample was then washed by centrifugation and decantation multiple times and air dried. The sample was split into two, one was clcined at 300°C for 2 hours and the other at 350°C for 1 hour, with anatase content estimated at 5-20% for the former and -10% for the latter.
Example 2a 6.13g of water was added to 12.27g TiOCl2 solution with stirring and cooling to below 25°C to obtain a To the diluted TiOCldiluted TiOCl2 solution. solution was added 54.00g of a solution comprising 10% by weight NaOH in water, with stirring and cooling to maintain a temperature below 25°C. This resulted in a suspension of white titanium containing precipitate of approximately pH 5. To this suspension was added 28.g of TiOCl2 solution, keeping the temperature below 25°C until the solution became completely transparent. To this transparent solution 0.925g of citric acid was added under stirring until the citric acid was dissolved. To this solution 102.035g of 10% NaOH solution was added resulting in a second suspension of titanium bearing precipitate at approximately pH 10. Stirring was continued for approximately 15 minutes after the last addition of 10% NaOH. The suspension was adjusted to approximately pH 4-5 with the addition of 4M HCl.
Approximately 200 ml of the second suspension was then placed into 4 x 50 ml centrifuge tubes and centrifuged and decanted multiple times for 2 minutes at 3000 rcf, each followed by addition of deionized water and re- suspension after each decantation. This was repeated until the NaCl content was substantially removed obtaining a washed precipitate comprising a titanate. The washed precipitate was then dried in air and ground to uniformity using an agate mortar and pestle to obtain a fine titanium dioxide powder with tap density approximately 1.2 g.cm*.
Example 2b The fine powdered titanium dioxide of example 2a was then subject to analysis by Raman microscopy and X-ray powder diffraction. These analyses indicated the finepowder was a titanium dioxide phase similar in structure to H-titanium dioxide or Na-titanium dioxide and free of any detectable anatase. Approximately O.3g of the fine powder was then heated in air at 350 °C for one hour to obtain a calcined powder sample. The calcined powder sample was then subject to analysis using Raman spectroscopy and x-ray powder diffraction, yielding curves indicating up to 5-20% anatase and 80- 95% bronze and minor NaCl. The sample was then analysed by energy dispersive x-ray analysis using a Zeiss SEM. The atomic titanium to sodium ratio (Ti/Na) was found to be 2.13:1 when subtracting away Na that was bonded to Cl in residual NaCl, here all Cl was assumed to be in NaCl, so the amount of Na subtracted from the total was equivalent to the atomic % of Cl.
Example 2c The calcined sample of Example 2b was washed to remove remaining soluble salt such that NaCl was not detected via XRD, and was then dried at 70 °C overnight. This sample was then analysed by Raman spectroscopy and found to have approximately 50% anatase and 50% bronze phases.
Example 2d By addition of a conducting material (carbon black, TIMCALWISUPER C65 Conductive Carbon Black) and a binder 10215), (a polyvinylidene fluoride, Kynar® PVDF RC- the dried sample of example 2c was made into an electrode and tested in an electrochemical half- cell. The composition was applied in a slurry was 8:1:1 active:carbon blackzbinder and the active loading of calcined material was between 2.7 and 3.mg cmfi. “Active” denotes the calcined material comprising titanium dioxide in bronze form. A copper foil of the electrode used was 20 um thick with average weight 16.1 mg cm*. The capacity at cyclewas approximately 92 mAh/g at C/10 and (see Figure 1) an approximately stable capacity of 80 mAh/g and a Coulombic efficiency levelling out at 100% after about -10 cycles out to 250 cycles at C/2 (see Figure 2).
Claims (28)
1. l. A method for manufacturing a TiO2 (B), titanium dioxide bronze material for a battery electrode material, the method comprising the steps of: a)providing an aqueous solution comprising TiOCl2, HCl, and an alpha-hydroxy acid, b) increasing' the pH of the solution until a precipitate is obtained, wherein the temperature is above 0 °C and below 55 °C, and c)calcining the obtained precipitate during a time range of 5 minutes to 48 hours at a temperature in the interval 300-450 °C to obtain a calcined material comprising the titanium dioxide bronze material.
2. The method according' to claim. l, wherein the aqueous solution comprising TiOCl2 is provided by at least partial hydrolysis of TiCl
3. The method according' to claim. l, wherein the aqueous solution comprising TiOCl2 is provided by dissolving' at least one titanic acid. with. the general formula TiOXMflD44X, wherein x is O or l, in an aqueous solution comprising at least one compound selected from the group consisting of TiOCl2, TiCl4, and HCl so that a clear solution is obtained, 30 °C. while keeping the temperature below
4. The method according to claim 3, wherein the at least one titanic acid is made from TiOCl2 by addition of an aqueous solution of a base until precipitation.
5. The method according to any one of claim 1-4, wherein. the obtained precipitate is washed. in water between steps b) and c).
6. The method according to any one of claim 1-5, wherein the method is carried out at a pressure p being ambient pressure f20%.
7. The method according to any one of claims 1-6, wherein pH is increased in step b) by addition of NaOH.
8. The method according to any one of claims 1-7, wherein the at least one alpha hydroxy acid is citric acid.
9. The method according to any one of claims 1-8, wherein the aqueous solution provided in step a) is clear.
10. The method according to any one of claims 1-9, wherein the precipitate is dried and optionally ground between steps b) and c).
11. The method according to any one of claims 1-9, wherein the obtained precipitate in step b) is separated from the remaining liquid between steps b) and c).
12. The method according to any one of claims 1-11, wherein at least one type of ions selected from the group consisting of Nat, Kt, Rb* and Cst, are added at any point before step c).
13. The method according to any one of claims 1-12, wherein Nb-ions are added at any point before step b).
14. The method according to any one of claims 1-13, wherein the pH in step b) is increased also after the precipitate is obtained and wherein the pH is increased to a value in the range 7-
15. The method according to any one of claims 1-14, wherein the calcined material is washed to reduce the content of soluble ions and then dried.
16. The method according to any one of claims 1-15, wherein at least one conducting material and least one binder is added to the calcined material to obtain an electrode material for a battery.
17. The method according to any one of claims 1-16, wherein at least one precursor for a conducting material is added before the calcination to obtain an electrode material for a battery.
18. The method according to claim 16, wherein the conducting material is carbon black.
19. The method according to claim 16 or 18, wherein the at least one conducting' material, the least one binder and the calcined material are mixed in a slurry.
20. The method according to any one of claims 16, 18 or 19, wherein the content of the calcined material in the electrode material is 70-90 wt%.
21. The method according to any one of claims 1-20, wherein a BET specific surface area of the calcined material according to ISA 9277 is in the range of 2-m2/g.
22. An electrode material for a battery manufactured. according' to the method. of any one of method claims 1-
23. The electrode material according to claim 22, wherein the material comprises a) 70-90 wt % of calcined titanium dioxide bronze having a BET specific surface area according to ISO 9277 in the range 2-30 HQ/g, and b) 30 - 10 wt% of a mixture of i) a conducting material and ii) a binder.
24. The electrode material according to any one of claims 22-23, wherein wt% ratio between the conducting material and the binder is in the range 1:1 to 7:
25. The electrode material according to any one of claims 22-24, wherein the conducting material is carbon black.
26. The electrode material according to any one of claims 22-25, wherein the titanium dioxide bronze comprises at least one type metal ion of selected from m metal group of sodium, potassium, caesium, rubidium, zinc, lanthanum, and tin.
27. A battery having an electrode comprising a titanium dioxide bronze material manufactured according to the method of any one of method claims 1-
28. The battery according to claim 27 wherein the BET specific surface area according to ISO 9277 is in the range 2-30 m2/g.
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| SE2050954A SE544708C2 (en) | 2020-08-14 | 2020-08-14 | Manufacture of a titanium dioxide bronze material for a battery electrode |
| SE2150677A SE546073C2 (en) | 2020-08-14 | 2021-05-27 | An electrode material and a battery comprising titanium dioxide bronze |
| PCT/EP2021/072633 WO2022034225A2 (en) | 2020-08-14 | 2021-08-13 | An electrode material and a battery as well as their manufacture |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130119306A1 (en) * | 2011-11-11 | 2013-05-16 | Min-Sang Song | Composite, method of manufacturing the composite, negative electrode active material including the composite, negative electrode including the negative electrode active material, and lithium secondary battery including the same |
| KR101752170B1 (en) * | 2016-12-22 | 2017-06-29 | 한국세라믹기술원 | Dispersion sol of rutile titanium dioxide and method for preparing the same |
| CN110040773A (en) * | 2019-04-11 | 2019-07-23 | 深圳市深清新型材料有限公司 | A kind of titanium oxide material and its application |
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2020
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130119306A1 (en) * | 2011-11-11 | 2013-05-16 | Min-Sang Song | Composite, method of manufacturing the composite, negative electrode active material including the composite, negative electrode including the negative electrode active material, and lithium secondary battery including the same |
| KR101752170B1 (en) * | 2016-12-22 | 2017-06-29 | 한국세라믹기술원 | Dispersion sol of rutile titanium dioxide and method for preparing the same |
| CN110040773A (en) * | 2019-04-11 | 2019-07-23 | 深圳市深清新型材料有限公司 | A kind of titanium oxide material and its application |
Non-Patent Citations (1)
| Title |
|---|
| Huang, Z. "Hydrolysis of Titanic acid in hydrochloric acid solutiob for syntheses of TiO2 powder with cotrolled particle size: Processes, morphology and kinetic study": University of Utha, Department of Metallurgical Engineering, December 2017 * |
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