A method for additive manufacturing comprising at least one thermochemical component

Abstract

The present invention relates to a method for additive manufacturing. The present invention also relates to an additive manufacturing apparatus for carrying out such a method for additive manufacturing. Furthermore, the present invention relates to a form stable thermochemical entity manufactured according to such a method and to the application thereof, namely in a heat storage or heat pump system.

Description

[0001]Title: A method for additive manufacturing comprising at least one thermochemical component Description: The present invention relates to a method for additive manufacturing. The present invention also relates to an additive manufacturing apparatus for carrying out such a method for additive manufacturing. Furthermore, the present invention relates to a form stable thermochemical entity manufactured according to such a method and to the application thereof, namely in a heat storage or heat pump system. International application WO 2019 / 038292 in the name of one of the present applicants discloses a closed-cycle thermal energy storage system comprising a thermochemical reactor containing a solid thermochemical material (TCM). In the TCM heat storage reaction, the TCM has two states, hydrous (discharged) and anhydrous (charged). The TCM charging involves the absorption of heat by the TCM and the release of sorbent gas. The TCM discharging involves the release of heat by the TCM and the sorption of a working gas or liquid. The main criteria of success for such storage technique are efficiency, energy density, power density, cost efficiency (short payback time), safety, and durability. International application WO2023001418 discloses an additive manufacturing process for manufacturing a sintered ceramic article, the method comprising the steps of providing a photopolymerizable slurry, selectively curing the photopolymerizable slurry to obtain a green body article, debinding the green body article to obtain a binderless body article, and d) sintering the binderless body article to obtain a sintered ceramic article. Dutch patent application NL 2035791 in the name of one of the present applicants and filed on September 13, 2023 relates to a system comprising a thermochemical material capable of storing and releasing heat by a thermochemical exchange process under release or binding of a gas or liquid, wherein the thermochemical material comprises particles, a plurality of particles being enclosed by a gas or liquid permeable material, the gas or liquid permeable material being impermeable for the thermochemical material. An article written by L. Tabard, E. Prud’Homme, V. Garnier, and L. Gremillard, “Hierarchical salt-ceramic composites for efficient thermochemical energy storage,” Appl. Mater. Today, vol. 20, p.100658, Sep. 2020, discloses a porous ceramic host material manufactured by a combination of additive fabrication process (robocasting) with a traditional pore-former method and partial sintering schedules, wherein ceria- stabilized zirconia is used as the host ceramic and magnesium sulphate as the active salt. This article discloses a ceramic porous matrix made with robot casting and subsequently charged by a salt through an impregnation method with a salt solution. This document is totally silent about combined additive manufacturing of a salt and a host material. US 2020 / 353681 relates to a slurry for additive manufacturing having a composition, comprising, inter alia, a monomer resin, a plurality of surrogate particles, a dispersant, a photoactivated dye, a photoabsorber, a photoinitiator and a diluent, wherein the surrogate particles are selected to represent a uranium-containing material and wherein the monomer resin is an acrylate-based monomer resin or a methacrylate-based monomer or mixtures thereof. These slurries and additive manufacturing processes can be used for in-situ volumetric inspection in which an additive manufacturing product includes a photoactivated dye component that is exposed to a light source, such as a ultraviolet-active dye component that is activated by exposure to an ultraviolet (UV) light to produce a signal that can be inspected for identification of manufacturing defects. EP 3299759 relates to a heat exchanger system for thermochemical storage and release, comprising a thermal exchange circuit with a heat exchanger fluid, the circuit further in thermal connection with a thermochemical module, the thermochemical module comprising a thermochemical material selected from the group consisting of zeolites, silica gel, hygroscopic salts, metal organic frameworks (MOF), carbon, and aluminum phosphates and / or their hydrates, that stores and releases heat by a thermochemical exchange process under release or binding of a sorbate, wherein the thermochemical module comprises a compartment structure that compartments the thermochemical material and further comprises a channel structure, to provide an exchange of the sorbate via the channel structure to the compartment structure. A wall structure comprising a polymeric material forms an interface between first and second channels, which wall structure is transgressive to the sorbate but retains the thermochemical material, wherein the polymeric material is cellulose, methylcellulose, ethylcellulose, cellulose acetate, or cellulose nitrate. Thermochemical entities that are now on the market are made by compression techniques like tabletting and compacting. High volume, industrial production faces a main challenge in guaranteeing high quality composite performance, and is confronted with material loss during production, relatively high energy use and sub-optimal CO2footprint. In addition such materials suffer from cyclic stability problems. Modern day manufacturing of stabilized salt hydrates is performed using different methods, such as encapsulation, impregnation or classical composite techniques using simple mixtures. However, these stabilized materials suffer from low energy density, power density and high costs. An object of the present invention is to provide thermochemical entities with well-defined geometry based on thermochemical material that have high cyclic form- stability with an enhanced high-power density. Another object of the present invention is to provide a method for obtaining well defined spatial positioning of composite constituents, resulting in performance control with a drastic reduction in material loss, energy, and CO2footprint. The present invention thus relates to a method for additive manufacturing comprising: - Providing a three-dimensional (3D) model data representing an object to be manufactured; - Generating a layer-wise toolpath based on the 3D model data; - Depositing a material layer onto a substrate according to the generated toolpath using an additive manufacturing apparatus, - curing the material layer thus deposited, and -repeating the steps of deposition and curing until the entire object is formed, wherein the composition of the material comprises at least one thermochemical component and at least one compatible host material. The present inventors found that for enhanced, high power output of a thermochemical composite, excellent mass and heat transfer is a prerequisite. To achieve this, a well-defined, and large, contact / surface area per volume is required, together with a well-defined accessible porosity, which has been realised by complex geometries. These complex geometries can be manufactured according to the present method as mentioned above. The present method can be seen as a one-pot additive manufacturing technique for manufacturing a form stable composite having a well defined geometry, a high surface area per volume and spatial positioning of the thermochemical material and other constituents. Due the geometry, which has been obtained by the present method of additive manufacturing, the material thus manufactured exhibits a high power and temperature output. In an embodiment the at least one thermochemical component is chosen from the group of AgF, Al2(SO4)3, Al2O3, Al4C3, AlCl3, AlF3, As2O5, AuCl3, Ba(ClO4)2, Ba(IO3)2, Ba(N3)2, Ba(OH)2, BaAl2O4, BaBr2, BaCl2, BaI2, BeSO4, Ca(ClO4)2, Ca(H2PO4)2, Ca(IO3)2, Ca(NO3)2, Ca(OH)2, CaBr2, CaCl2, CaC2O4, CaHPO4, CaSeO4, CaSiF6, CaSO3, CaSO4, CaTeO3, Cd(ClO4)2, Cd(NO3)2, CdBr2, CdCl2, CdSO4, Ce(SO4)2, CeCl3, CePO4, CH3NH2Al(SO4)2, CH3NH2ACrSO4)2, CH3NH2Fe(SO4)2, Co(ClO4)2, Co(NO3)2, CoBr2, CoCl2, CoSO4, Cr2(SO4)3, CrCl2, Cs2CO(SO4)2, Cs2CO3, CsAl(SO4)2,CsCd(SO4)2, CsCo(SO4)2,CsCr(SeO4)2,CsCr(SO4)2,CsF, CsFe(SO4)2, CsMg(SO4)2, CsNi(SO4)2, CsTi(SO4)2, CsV(SO4)2, CsZn(SO4)2, Cu(ClO4)2, Cu(IO3)2, Cu(NO3)2, Cu3(PO4)2, CuBr2, CuCl2, CuF2, CuHPO4, CuSeO3, CuSO4, DyCl3, CyPO4, ErCl3, ErPO4, Eu(IO3)3, EuCl3EuPO4, FeBr2, FeCl2,FeCl3, FeI2,fePO4, FeSO4, GdCl3, GdPO4, H2C2O4, H2SeO3, H2SO4, HIO3, HoPO4, K2C2O4,KHCO3, K2C4H4O6, K2CO(SO4)2, K2CO3, K2CuCl4, K2Fe(SO4)2, K2Mg(SO4)2, K2Mn(SO4)2, K2Ni(SO4)2, K2Zn(SO4)2,K2SO3, K3PO4, K4Fe(CN)6, K4P2O7, KAl(SO4)2, KF, KOH, LaCl3, LaPO4, Li2SO4, LiBr, LiCl, LiClO4, LiI, LiNO2, LiNO3, LiOH, LuCl3, LuPO4, Mg(ClO4), Mg(NO3)2, MgBr2, MgCl2, MgCO3, MgCO3, MgSeO3, MgSeO4,MgSO3, MgSO4,MgTeO3,Mn(ClO4)2, MnBr2, MnCl2, MnF2, MnI2, MnSeO4, MnSO4,MoO3, Na0.96Al0.96Si2.04O6, Na2B4O7, Na2C2H4O6, Na2CO3Na2CrO4, Na2HAsO4, Na2HPO4, Na2S, Na2S2O3, Na2SiO3, Na2SO3, Na2SO4, Na2WO4, Na3PO4, Na4P2O7, NaAl(SO4)2, NaBr, NaC2H3O2, NaClO2, NaClO4, NaCN, NaCr(SO4)2, NaHC2O4, NaHSO4, NaI, NaIO3, NaKC4H4O6, NaOH, Nd2(SO4)3, NdCL3, NdPO4, (NH2OH) Al(SO4)2, NH2OH) Cr(SO4)2, (NH4)2Co(SO4)2, (NH4)2Mg(SO4)2, (NH4)2Zn(SO4)2, (NH4) V(SO4)2, NH4(UO2)2F5, NH4(UO2)2F5, NH4Al(SO4)2, NH4Co(SO4)2, NH4Cr(SO4)2, NH4Fe(SO4)2, Ni(ClO4)2, Ni(IO3)2, Ni(NO3)2, NiCl2NiSO4, Pb(CH3CO2)2, PrCl3, PtCL4, PuCl3, PuO2(OH)2, Ra(BrO3)2, Ra(IO3)2, RaBr2, RaCl2, RaI2, Rb2Cd(SO4)2, Rb2CO3, Rb2Mg(SO4)2, Rb2Mn(SO4)2, Rb2Ni(SO4)2, Rb2Zn(SO4)2, Rb2Al(SO4)2, Rb2Cr(SO4)2, Rb2Fe(SO4)2, RbF, RbOH, RbTi(SO4)2, RbV(SO4)2, ScCl3, SmCl3, SmPO4, Sr(BrO3)2, Sr(IO3)2, Sr(NO3)2, Sr(OH)2, SrBr2, SrCl2, SrTeO3, TbCL3, TbPO4, Tc2O7, Th(NO3)4, ThF4, Ti(Al(SO4))2, Ti(Cr(SO4))2, TiOH, TmPO4, U(SO4)2, UF4, (UO2)3(PO4)2, UO2(NO3)2, UO2(OH)2, UO2Br2, UO2Cl2, UO2F2, UO2SO4, UO3, UOF2, UOFOH, V2O5, VOSO4, YbPO4, YCl3, YPO4, Zn(ClO4)2, Zn(NO3)2, ZnBr2, ZnCl2, ZnF2,ZnSO4, and its hydrate, ammoniate, alcoholate, and carbonation derivatives, silica (gels) amorphous and crystalline, metal organic frameworks, zeolites, (natural) clays, vermiculite, and activated carbon. The above mentioned group of thermochemical components also includes derivatives and modified materials on the basis of that list of thermochemical components. For metal salts, the molecular substitution can either replace all the metal and / or counter ions with a different ion, or only partially replace. Other derivatives can include a material having intercalated ions or having different species present at the material surface. Such different species at the surface can also be classified as additives. In an embodiment the at least one compatible host material is chosen from the group of acrylamides, acrylic esters, acrylic polymers, methacrylic polymers, siloxanes, stearyl esters, nylons, metals powders, nylon powders, polymer powders, epoxy resins, PLA, PVA, PVC, urethanes, PP, PE, PETG, UV-curable or radical curable monomers and polymers. In another embodiment the at least one thermochemical component is chosen from the group of CaCl2, SrCl2, SrBr2,K2CO3, CaC2O4, silica gels and zeolites. In another embodiment the at least one compatible host material is chosen from the group of polymer powders, UV-curable or radical curable monomers and polymers. In another embodiment the composition of the material comprises a combination of CaC2O4as thermochemical component and one of the group of polymer powders, UV-curable or radical curable monomers and polymers as compatible host material. In an embodiment the composition of the material further comprises heat conductive materials, such as metal powders and flakes, for example aluminium, copper, silver and graphite, ceramic fillers, for example aluminium oxide, boron nitride and silicon carbide, carbon fibers and carbon nanotubes. In an embodiment the composition of the material further comprises one or more of polymer, non-ionic surfactants, ionic surfactants and other dispersing, pore forming, and stabilizing agents. In an embodiment of the method for additive manufacturing as discussed above the material layer is deposited by selectively melting a solid material. In an embodiment of the method for additive manufacturing as discussed above the material layer is deposited by extruding a filamentary material. In an embodiment of the method for additive manufacturing as discussed above the material layer is deposited by printing a liquid material. In an embodiment of the method for additive manufacturing as discussed above the material layer is deposited by curing a liquid material. The present invention also relates to a system comprising an additive manufacturing apparatus and a material, said additive manufacturing apparatus comprising: A controller configured to receive and process three-dimensional (3D) model data; A deposition system configured to deposit material layer by layer based on the processed 3D model data; and A substrate platform configured to support the object being manufactured, wherein the composition of the material comprises at least one thermochemical component and at least one compatible host material. In an embodiment the deposition system comprises a system for depositing material layer by layer based on the processed 3D model data, such as fused filament fabrication (FFF), direct ink writing (DIW), selective laser sintering (SLS), stereolithography (SLA) and digital light processing (DLP). The present invention relates to a form stable thermochemical entity manufactured according to a method as discussed above, wherein the thermochemical entity comprises at least one thermochemical component and at least one compatible host material, the form stable thermochemical entity having a power density in the order of at least 30 kW / m3, preferably at least >100kW / m3, more preferably at least 300 kW / m3. The power density is measured as total uptake moles of water / second multiplied by the reaction enthalpy and divided by the samples volume. In addition, the present invention relates to a heat storage system comprising at least a form stable thermochemical entity as discussed above. According to an example the heat storage system is a heat battery based on thermochemical principles. Furthermore, the present invention relates to the use of a form stable thermochemical entity as discussed above in convective thermochemical systems and in vacuum systems for obtaining a stable system performance including power output with charging and discharging cycles. The present invention relates to the use of a form stable thermochemical entity as discussed above in a chemical heat pump. The present method as discussed above can be seen as a one-pot additive manufacturing method for manufacturing a form stable thermochemical entity. Due to the nature of the present additive manufacturing method a range of geometries containing a thermochemical material can be manufactured. Additionally, the present additive manufacturing method enables a controlled spatial distribution of composite constituents, e.g. heat conductive materials having a well distributed and well-defined position can be directly integrated into the host material resulting in enhanced heat transfer properties. The benefits thereof are a drastic power enhancement on composite, and composite bed level, new thermochemical applications, such as thermochemical heat pumps, improved heat storage applications both atmospheric and vacuum systems in terms of power output and geometry, and reduction in energy consumption and waste production compared to standard manufacturing techniques such as compacting, impregnation, encapsulation and tableting. The enclosed figure 1 shows two examples of two prototype composites manufactured according to the present one-pot manufacturing additive method. The invention will be explained in more detail with the following figure and examples, without being restricted thereto. As an additive manufacturing apparatus Anycubic Photon Mono 4K was used. The host material was an acrylate-based UV resin, i.e. Druckwege High Temp Resin. Example 1: manufacturing of a spherical entity In this example the thermochemical component was calcium oxalate. Prior to the step of printing calcium oxalate was mixed into the resin material (10%) and properly stirred for 15 minutes. After printing the material was washed five times with isopropanol and left to completely cure at ambient conditions for 48 hours. It is also fully stable at ambient conditions (no deliquescence). Dehydration was performed at 160 °C, and rehydration was performed at 33% RH. The form stable thermochemical entity thus manufactured has a power density of 320 kW / m3. Example 2: manufacturing of a cylindrical entity In this example the thermochemical was K2CO3. Prior to the step of printing K2CO3was mixed (10%) into the resin material and properly stirred for 15 minutes. After printing the material was washed five times with isopropanol and left to completely cure at 33% RH conditions for 48 hours. Dehydration was performed at 130 °C, and rehydration was performed at 33% RH. The form stable thermochemical entity thus manufactured has a power density of 100 kW / m3. Example 3: manufacturing of a cylindrical entity In this example the thermochemical component was calcium oxalate. Prior to the step of printing calcium oxalate was mixed into the resin material (10%) and properly stirred for 15 minutes. After printing the material was washed five times with isopropanol and left to completely cure at ambient conditions for 48 hours. It is also fully stable at ambient conditions (no deliquescence). Dehydration was performed at 160 °C, and rehydration was performed at 33% RH. The form stable thermochemical entity thus manufactured has a power density of 320 kW / m3. Example 4: manufacturing of a spherical entity In this example the thermochemical was K2CO3. Prior to printing K2CO3was mixed (10%) into the resin material and properly stirred for 15 minutes. After printing the material was washed five times with isopropanol and left to completely cure at 33% RH conditions for 48 hours. Dehydration was performed at 130 °C, and rehydration was performed at 33% RH. The form stable thermochemical entity thus manufactured has a power density of 100 kW / m3. Example 5: manufacturing of a porous cubical entity. In this example the thermochemical component was calcium oxalate. Prior to the step of printing calcium oxalate was mixed into the acrylate resin material (20%) and mechanically stirred for 5 minutes. After printing the material was washed five times with isopropanol and left to completely cured in a UV curing device for 60 seconds. The form stable thermochemical entity thus manufactured has a power density of 325 kW / m3. Example 6: manufacturing of a porous cubical entity. In this example the thermochemical component was calcium oxalate. Prior to the step of printing calcium oxalate was mixed into the acrylate resin material (15%) and mechanically stirred for 5 minutes. The acrylate resin contained additives to render it thermally stable up to 200 deg. C. After printing the material was washed five times with isopropanol and left to completely cured in a UV curing device for 60 seconds. The form stable thermochemical entity thus manufactured has a power density of 300 kW / m3. Example 7: manufacturing of a porous cubical entity. In this example the thermochemical component was calcium oxalate. Prior to the step of printing calcium oxalate was mixed into the acrylate resin material (40%) and mechanically stirred for 5 minutes. The acrylate resin contained additives to render it thermally stable up to 200 deg. C. After printing the material was washed five times with isopropanol and left to completely cured in a UV curing device for 60 seconds. It is also fully stable at ambient conditions (no deliquescence). Dehydration was performed at 160 °C, and rehydration was performed at 33% RH. The form stable thermochemical entity thus manufactured has a power density of 350 kW / m3. Example 8: manufacturing of a porous cubical entity. In this example the thermochemical component was calcium oxalate. Prior to the step of printing calcium oxalate (30%) was mixed into the epoxy / acrylate resin material together with a dispersant additive (Triton X-100, 1%) and mechanically stirred for 5 minutes. After printing the material was washed five times with isopropanol and left to completely cured in a UV curing device for 60 seconds. It is also fully stable at ambient conditions (no deliquescence). Dehydration was performed at 160 °C, and rehydration was performed at 33% RH. The form stable thermochemical entity thus manufactured has a power density of 300 kW / m3. Example 9: manufacturing of a porous cubical entity. In this example the thermochemical component was calcium oxalate. Prior to the step of printing calcium oxalate (30%) was mixed into the epoxy / acrylate resin material together with a dispersant additive (Triton X-100, 2%) and mechanically stirred for 5 minutes. After printing the material was washed five times with isopropanol and left to completely cured in a UV curing device for 60 seconds. It is also fully stable at ambient conditions (no deliquescence). Dehydration was performed at 160 °C, and rehydration was performed at 33% RH. The form stable thermochemical entity thus manufactured has a power density of 350 kW / m3. Example 10: manufacturing of a porous cubical entity. In this example the thermochemical component was calcium oxalate. Prior to the step of printing calcium oxalate (30%) was mixed into the epoxy / acrylate resin material together with a dispersant additive (Triton X-100, 5%) and mechanically stirred for 5 minutes. After printing the material was washed five times with isopropanol and left to completely cured in a UV curing device for 60 seconds. It is also fully stable at ambient conditions (no deliquescence). Dehydration was performed at 160 °C, and rehydration was performed at 33% RH. The form stable thermochemical entity thus manufactured has a power density of 400 kW / m3. In Examples 8-10 a dispersant additive was mixed into the mixture of the thermochemical component and the compatible host material. The present inventors found that such a dispersant additive results in a better dispersion of the thermochemical component in the compatible host material. Such better dispersion results in less agglomerates, this gives higher accessible surface area and therefore higher power density.

Claims

CLAIMS 1. A method for additive manufacturing comprising: - Providing a three-dimensional (3D) model data representing an object to be manufactured; - Generating a layer-wise toolpath based on the 3D model data; - Depositing a material layer onto a substrate according to the generated toolpath using an additive manufacturing apparatus, - curing the material layer thus deposited, and -repeating the steps of deposition and curing until the entire object is formed, wherein the composition of the material comprises at least one thermochemical component and at least one compatible host material.

2. A method for additive manufacturing according to claim 1, wherein the at least one thermochemical component is chosen from the group of AgF, Al2(SO4)3, Al2O3, Al4C3, AlCl3, AlF3, As2O5, AuCl3, Ba(ClO4)2, Ba(IO3)2, Ba(N3)2, Ba(OH)2, BaAl2O4, BaBr2, BaCl2, BaI2, BeSO4, Ca(ClO4)2, Ca(H2PO4)2, Ca(IO3)2, Ca(NO3)2, Ca(OH)2, CaBr2, CaCl2, CaC2O4, CaHPO4, CaSeO4, CaSiF6, CaSO3, CaSO4, CaTeO3, Cd(ClO4)2, Cd(NO3)2, CdBr2, CdCl2, CdSO4, Ce(SO4)2, CeCl3, CePO4, CH3NH2Al(SO4)2, CH3NH2ACrSO4)2, CH3NH2Fe(SO4)2, Co(ClO4)2, Co(NO3)2, CoBr2, CoCl2, CoSO4, Cr2(SO4)3, CrCl2, Cs2CO(SO4)2, Cs2CO3, CsAl(SO4)2,CsCd(SO4)2, CsCo(SO4)2,CsCr(SeO4)2,CsCr(SO4)2,CsF, CsFe(SO4)2, CsMg(SO4)2, CsNi(SO4)2, CsTi(SO4)2, CsV(SO4)2, CsZn(SO4)2, Cu(ClO4)2, Cu(IO3)2, Cu(NO3)2, Cu3(PO4)2, CuBr2, CuCl2, CuF2, CuHPO4, CuSeO3, CuSO4, DyCl3, CyPO4, ErCl3, ErPO4, Eu(IO3)3, EuCl3EuPO4, FeBr2, FeCl2,FeCl3, FeI2,fePO4, FeSO4, GdCl3, GdPO4, H2C2O4, H2SeO3, H2SO4, HIO3, HoPO4, K2C2O4,KHCO3, K2C4H4O6, K2CO(SO4)2, K2CO3, K2CuCl4, K2Fe(SO4)2, K2Mg(SO4)2, K2Mn(SO4)2, K2Ni(SO4)2, K2Zn(SO4)2,K2SO3, K3PO4, K4Fe(CN)6, K4P2O7, KAl(SO4)2, KF, KOH, LaCl3, LaPO4, Li2SO4, LiBr, LiCl, LiClO4, LiI, LiNO2, LiNO3, LiOH, LuCl3, LuPO4, Mg(ClO4), Mg(NO3)2, MgBr2, MgCl2, MgCO3, MgCO3, MgSeO3, MgSeO4,MgSO3, MgSO4,MgTeO3,Mn(ClO4)2, MnBr2, MnCl2, MnF2, MnI2, MnSeO4, MnSO4,MoO3, Na0.96Al0.96Si2.04O6, Na2B4O7, Na2C2H4O6, Na2CO3 Na2CrO4, Na2HAsO4, Na2HPO4, Na2S, Na2S2O3, Na2SiO3, Na2SO3, Na2SO4, Na2WO4, Na3PO4, Na4P2O7, NaAl(SO4)2, NaBr, NaC2H3O2, NaClO2, NaClO4, NaCN, NaCr(SO4)2, NaHC2O4, NaHSO4, NaI, NaIO3, NaKC4H4O6, NaOH, Nd2(SO4)3, NdCL3,NdPO4, (NH2OH) Al(SO4)2, NH2OH) Cr(SO4)2, (NH4)2Co(SO4)2, (NH4)2Mg(SO4)2, (NH4)2Zn(SO4)2, (NH4) V(SO4)2, NH4(UO2)2F5, NH4(UO2)2F5, NH4Al(SO4)2, NH4Co(SO4)2, NH4Cr(SO4)2, NH4Fe(SO4)2, Ni(ClO4)2, Ni(IO3)2, Ni(NO3)2, NiCl2NiSO4, Pb(CH3CO2)2, PrCl3, PtCL4, PuCl3, PuO2(OH)2, Ra(BrO3)2, Ra(IO3)2, RaBr2, RaCl2, RaI2, Rb2Cd(SO4)2, Rb2CO3, Rb2Mg(SO4)2, Rb2Mn(SO4)2, Rb2Ni(SO4)2, Rb2Zn(SO4)2, Rb2Al(SO4)2, Rb2Cr(SO4)2, Rb2Fe(SO4)2, RbF, RbOH, RbTi(SO4)2, RbV(SO4)2, ScCl3, SmCl3, SmPO4, Sr(BrO3)2, Sr(IO3)2, Sr(NO3)2, Sr(OH)2, SrBr2, SrCl2, SrTeO3, TbCL3, TbPO4, Tc2O7, Th(NO3)4, ThF4, Ti(Al(SO4))2, Ti(Cr(SO4))2, TiOH, TmPO4, U(SO4)2, UF4, (UO2)3(PO4)2, UO2(NO3)2, UO2(OH)2, UO2Br2, UO2Cl2, UO2F2, UO2SO4, UO3, UOF2, UOFOH, V2O5, VOSO4, YbPO4, YCl3, YPO4, Zn(ClO4)2, Zn(NO3)2, ZnBr2, ZnCl2, ZnF2,ZnSO4, and its hydrate, ammoniate, alcoholate, and carbonation derivatives, silica (gels) amorphous and crystalline, metal organic frameworks, zeolites, (natural) clays, vermiculite, and activated carbon.

3. A method for additive manufacturing according to any one of claims 1-2, wherein the at least one compatible host material is chosen from the group of acrylamides, acrylic esters, acrylic polymers, methacrylic polymers, siloxanes, stearyl esters, nylons, metals powders, nylon powders, polymer powders, epoxy resins, PLA, PVA, PVC, urethanes, PP, PE, PETG, UV-curable or radical curable monomers and polymers.

4. A method for additive manufacturing according to any one of claims 2-3, wherein the at least one thermochemical component is chosen from the group of CaCl2, SrCl2, SrBr2,K2CO3, CaC2O4,silica gels and zeolites.

5. A method for additive manufacturing according to any one of claims 2-4, wherein the at least one compatible host material is chosen from the group of polymer powders, UV-curable or radical curable monomers and polymers.

6. A method for additive manufacturing according to any one of claims 2-5, wherein the composition of the material comprises a combination of CaC2O4as thermochemical component and one of the group of polymer powders, UV-curable or radical curable monomers and polymers as compatible host material.

7. A method for additive manufacturing according to any one of claims 1-6, wherein the composition of the material further comprises heat conductive materials, such as metal powders and flakes, for example aluminium, copper, silver and graphite,ceramic fillers, for example aluminium oxide, boron nitride and silicon carbide, carbon fibers and carbon nanotubes.

8. A method for additive manufacturing according to any one of claims 1-7, wherein the composition of the material further comprises one or more of polymer, non-ionic surfactants, ionic surfactants and other dispersing, pore forming, and stabilizing agents.

9. A method for additive manufacturing according to any one of claims 1-8, wherein the material layer is deposited by selectively melting a solid material.

10. A method for additive manufacturing according to any one of claims 1-8, wherein the material layer is deposited by extruding a filamentary material.

11. A method for additive manufacturing according to any one of claims 1-8, wherein the material layer is deposited by printing a liquid material.

12. A method for additive manufacturing according to any one of claims 1-8, wherein the material layer is deposited by curing a liquid material.

13. A system comprising an additive manufacturing apparatus and a material, said additive manufacturing apparatus comprising: A controller configured to receive and process three-dimensional (3D) model data; A deposition system configured to deposit material layer by layer based on the processed 3D model data; and A substrate platform configured to support the object being manufactured, wherein the composition of the material comprises at least one thermochemical component and at least one compatible host material.

14. A system according to claim 13, wherein the deposition system comprises a system for depositing material layer by layer based on the processed 3D model data, such as fused filament fabrication (FFF), direct ink writing (DIW), selective laser sintering (SLS), stereolithography (SLA) and digital light processing (DLP).

15. A form stable thermochemical entity manufactured according to a method according to any one or more of claims 1-12, wherein the thermochemical entity comprises at least one thermochemical component and at least one compatible host material, the form stable thermochemical entity having a power density in the order of at least 30 kW / m3, preferably at least >100kW / m3, more preferably at least 300 kW / m3.

16. A heat storage system comprising at least a form stable thermochemical entity according to claim 15.

17. A heat storage system according to claim 16, wherein the heat storage system is a heat battery based on thermochemical principles.

18. The use of a form stable thermochemical entity according to claim 15 in convective thermochemical systems and in vacuum systems for obtaining a stable system performance including power output with charging and discharging cycles.

19. The use of a form stable thermochemical entity according to claim 15 in a chemical heat pump.

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