Let $\Omega$ be a domain in $\mathbb R^3$ and let $\pi_2(\Omega)$ be the second homotopy group of $\Omega$. Let $\mathbf{F}=(P,Q,R)$ be a $C^1$ vector field. If $\pi_2(\Omega)=0$, can we deduce that the surface integral $$\iint\limits_{\Sigma}Pdydz+Qdzdx+Rdxdy$$ has nothing to do with the surface $\Sigma$, but only with its boundary curve of $\Sigma$ if and only the divergence of $\mathbf{F}$ is zero, that is $$\frac{\partial P}{\partial x}+\frac{\partial Q}{\partial y}+\frac{\partial R}{\partial z}=0.$$
Here has nothing to do with the surface $\Sigma$ means that if $\widetilde{\Sigma}$ is another surface and they has the same boundary curve $$\partial\Sigma=\partial\widetilde{\Sigma},$$ then $$\iint\limits_{\Sigma}Pdydz+Qdzdx+Rdxdy=\iint\limits_{\widetilde{\Sigma}}Pdydz+Qdzdx+Rdxdy.$$
In other words, can $\pi_2(\Omega)=0$ implies the second de Rham cohomology group is zero? Here $\Omega$ is a domain in $\mathbb R^3$.
Since @Kevin.S has already established that you can have a region $\Omega$ with $\pi_2(\Omega) = 0$ and $H^2(\Omega)=\Bbb R$ and you've raised a good question in the comments, let me address that question.
Let $\Omega = \{(x,y,z): 1\le \left(\sqrt{x^2+y^2}-3\right)^2+z^2 \le 4\}$. Let $\Sigma = \Sigma_+\cup\Sigma_-$ be the torus $\Sigma = \{(x,y,z): \left(\sqrt{x^2+y^2}-3\right)^2+z^2 = 2\}$, and let $\Sigma_+ = \Sigma \cap \{y\ge 0\}$ and $\Sigma_- = \Sigma\cap\{y\le 0\}$ with their induced orientations. Note that $\partial\Sigma_+ = -\partial\Sigma_-$.
If we let $\omega$ be the standard area $2$-form of $\Sigma$. Then $\int_{\Sigma_+} \omega = \int_{\Sigma_-} \omega = 2\pi^2$. As we already pointed out, $\partial\Sigma_+ = -\partial\Sigma_-$, but $$\int_{\Sigma_+} \omega = 2\pi^2 = -\int_{-\Sigma_-} \omega,$$ so there's an example you wanted.
If you think of the torus as $S^1\times S^1$, you get naturally get $\omega = d\theta_1\wedge d\theta_2$. If you want Cartesian coordinates, I offer you this: $$\omega = \frac{-z\,dx + (x-3)\,dz}{(x-3)^2+z^2}\wedge\frac{-y\,dx+x\,dy}{x^2+y^2}.$$